Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same

ABSTRACT

Compounds and methods of preparing compounds of the formula:  
     RZ—CO—CR a R b —(CR c R d ) n —NH—(Y) m —CO—A  (I)  
     wherein n is an integer from 1 to 15, m is either 0 or 1; R a , R b , R c , and R d  are each a hydrogen or a hydrocarbyl group; Y is CO—(CR e R f ) p , wherein R e  and R f  are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C 6 H 4 —, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group; Z is —O— or —NG—, wherein G is H, C 1 -C 12  alkyl or the radical R; wherein R is  
                 
 
     wherein R 1  is hydrogen, C 1 -C 18  alkyl, O, OH, CH 2 CN, C 1 -C 18  alkoxy, C 1 -C 18  hydroxyalkoxy, C 5 -C 12  cycloalkoxy, C 5 -C 12  hydroxycycloalkoxy, C 3 -C 6  alkenyl, C 1 -C 18  alkynyl, C 7 -C 9  phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C 1 -C 4  alkyls, or an aliphatic C 1 -C 8  acyl; R 2  is hydrogen, C 1 -C 8  alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6  are each a hydrogen, C 1 -C 8  alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C 5 -C 10  cycloalkyl; and A is either ZR or a hydrocarbyl group, which are useful for stabilizing polymer compositions against photo- and thermal degradation

[0001] This application is a continuation-in-part of U.S. applicationSer. No. 09/704,793, filed Nov. 3, 2000.

FIELD OF THE INVENTION

[0002] This invention relates generally to novel hindered amine lightstabilizers (HALS) and their use as a protectant against ultravioletradiation or light (“UV light”). Also included are concentrates andarticles including such stabilizers, and methods of making all of theabove.

BACKGROUND

[0003] It is well known that ultraviolet (“UV”) light or radiation,especially sunlight, can cause degradation of a variety of materials,especially polymeric materials. Often this results in embrittlement oryellowing of the materials, which may be in the form of molded articles,extruded articles, films, tapes, coatings, or the like. However, thisdegradation can be inhibited by the incorporation of light stabilizersin, or on, the polymeric articles. The most commonly used stabilizersare UV-absorbers, hindered amine light stabilizers (“HALS”), andphenolic and non-phenolic antioxidants.

[0004] HALS scavenge free radicals formed in polymeric material when thematerial is exposed to UV light. The functional component of the HALSmolecule is typically the 2,2,6,6-tetraalkylpiperidine moiety.Typically, the 2,2,6,6-tetraalkylpiperidine moiety is anchored to acarbonyl or melamine functional group (See, e.g., U.S. Pat. Nos.4,331,586; 3,840,494; Re. 31,342; Re. 30,385; 3,640,928; 4,086,204;4,265,805). Anchoring the 2,2,6,6-tetraalkylpiperidine moiety to acarbonyl or melamine functional group typically lowers the volatilityand extractability of a stabilizer. Low volatility is an importantcharacteristic of light stabilizers in applications where hightemperatures are encountered, which occurs frequently in the processingof thermoplastics and in the curing of thermoset resins and coatings.Often, high temperatures are also present in the end-use applicationsfor the stabilized material. Low volatility helps prevent loss of thestabilizer during processing, curing, and high temperature end uses.Typically, HALS molecules containing the 2,2,6,6-tetraalkylpiperidinegroup anchored to a carbonyl group are made by reacting a2,2,6,6-tetraalkylpiperidin-4-ol or4-amino-2,2,6,6-tetramethylpiperidine with a carboxylic acid chloride orester.

[0005] U.S. Pat. Nos. Re. 31,342, 4,021,432 and 4,049,647 disclose aclass of 1- and 4-substituted piperidines that are stabilizers fororganic materials. The stabilizers are produced by reacting thecorresponding 1-substituted piperidinols with acid chlorides, or thecorresponding 4-substituted piperidines, with a compound introducing aresidue into the 1-position of the piperidine moiety.

[0006] U.S. Pat. No. 3,840,494 discloses a polymer compositionstabilized against photo- and thermal deterioration by incorporatingtherein acid esters of 4-piperidinol derivatives in an amount sufficientto prevent such deterioration. The acid esters of the 4-piperidinolderivatives are prepared by reacting the 4-piperidinol derivative with acarboxylate ester in xylene with sodium hydroxide. For example, thereaction of 4-hydroxy-2,2,6,6-tetramethylpiperidine with ethyl benzoateproduces 4-benzoyloxy-2,2,6,6-tetramethylpiperidine.

[0007] Similarly, the 2,2,6,6-tetramethylpiperidin-4-ol can be reactedwith diesters or diacid chlorides to produce diester-HALS. Also, the2,2,6,6-tetramethylpiperidin-4-ol can be reacted with a diisocyanate toproduce a diurethane-HALS. However, the relatively high cost ofdiisocyanates makes them less practical than diesters when preparingHALS.

[0008] Compounds which have an ester functionality at one terminus of ahydrocarbon chain and a urethane functionality at the other terminus ofthe hydrocarbon chain (alkoxycarbonylamino alkanoates) are known forvarious other uses other than light stabilization and can be prepared bya variety of synthetic schemes (See, e.g., Effenberger, F.; Drauz, K.;Foerster, S.; Mueller, W., Chem. Ber., 114(1), 173-89; Dixit, A.;Tandel, S.; Rajappa, S.; Tett. Lett.; 35(33), 6133-4, Duong, et al.,Aust. J. Chem., 29, 2651-61, 1976; Iwaka et al., J. Org. Chem., 31,142-46, 1966; Taub; Hino; J. Chem. Eng. Data, 9, 106, 1964; U.S. Pat.No. 5,300,678 to Merger et al.).

[0009] U.S. Pat. No. 5,574,162 discloses 1-hydrocarbyloxy substitutedHALS, which also contain reactive functional groups that chemicallyattach to selected polymer substrates by condensation reactions.

[0010] Oligomeric HALS are also known. For example, TINUVIN 622 is acommercially available oligomeric HALS produced by Ciba SpecialtyChemicals Inc. of Hawthorne, N.Y. TINUVIN 622 can be produced by thereaction of dimethyl succinate withN-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol. U.S. Pat. No.4,223,412 discloses condensation and addition polymers wherein therecurrent molecular unit contains a polyalkylpiperidine radical that areuseful as light stabilizers for plastics. In one embodiment thecopolymer is formed by copolymerization or copolycondensation ofpolyalkylpiperidine containing monomers with polyalkylpiperidine freemonomers such as caprolactam.

[0011] U.S. Pat. No. 6,271,377 discloses HALS which are substituted onthe N-atom by N-alkyloxy moieties containing one to three hydroxylgroups.

[0012] U.S. Pat. No. 4,331,586 to Hardy discloses oligomers that containat least one piperidyl moiety in the repeating unit for use as lightstabilizers. While providing protection for polymeric materials, such aspolypropylene, polymeric films containing the disclosed oligomeric HALSbecame brittle after exposure to UV light for about 1,700 hours.

[0013] HALS compounds may be used individually or in combination withother light stabilizers to inhibit photodegradation of polymers. Forexample, UV light absorbers, such as benzotriazoles and benzophenones,were initially used to stabilize polymeric materials and to preventdegradation of such materials from exposure to UV light. Later, it wasdiscovered that HALS compounds were more effective than UV lightabsorbers alone, and thus, UV light absorbers are presently used incombination with at least one HALS compound in most conventionalapplications (See, e.g., U.S. Pat. Nos. 4,740,542; 4,619,956; 5,461,151;5,721,298). Similarly, HALS compounds are often employed in combinationwith other stabilizers, such as antioxidants (See, e.g., U.S. Pat. No.4,722,806). Combining the HALS with another stabilizer may provide apolymeric material with better resistance to weathering.

[0014] U.S. Pat. No. 4,619,956 discloses a method of stabilizing apolymer film, coating, or molded article against the action of light,moisture and oxygen by incorporating a HALS compound and atris-aryl-s-triazine UV light absorber into a polymer. Preferably, theHALS compound is a 2,2,6,6-tetraalkylpiperidine compound, salt, or metalcomplex, and the UV light absorber is a tris-aryl-2-triazine of formula

[0015] where X, Y, and Z are each aromatic carbocyclic groups, and atleast one of the aromatic groups has a hydroxy group ortho to the pointof attachment to the triazine ring. Each of R¹ to R⁹ is hydrogen,hydroxy, alkyl, alkoxy, sulfonic, carboxy, halo, haloalkyl, oracylamino. Each of the UV light absorbers and HALS compound are used inan amount of from about 0.01 to 5 percent by weight, but onlyformulations having equal amounts of UV light absorber and HALS compoundare exemplified. The compositions are effective in stabilizing thepolymeric material, which does not begin to lose gloss or turn yellowuntil after about 1,000 to 2,400 hours of exposure to UV light.

[0016] Thus, a need still remains for improved articles, andcompositions and methods of use and preparation thereof, that stabilizepolymeric materials and provide protection from exposure to UV light forextended periods of time. The present invention provides suchcompositions, articles and methods.

SUMMARY OF THE INVENTION

[0017] The invention provides a new class of HALS. The HALS of theinvention have the formula (I):

RZ—CO—RC^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH—(Y)_(m)—CO—A  (I)

[0018] wherein n is an integer from 1 to 15, m is either 0 or 1; R^(a),R^(b), R^(c), and R^(d) are each a hydrogen or a hydrocarbyl group; Y isCO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f) are each a hydrogen orhydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C₆H₄—,wherein the substitution pattern on the phenylene group is an ortho,meta, or para substitution pattern and one or more of the hydrogens ofthe phenylene group may be substituted by a hydrocarbyl group or afunctional group; Z is —O— or —NG—, wherein G is H, C₁-C₁₂ alkyl or theradical R; wherein R is

[0019] wherein R¹ is hydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂hydroxycycloalkoxy, C₃-C₆ alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl,unsubstituted or substituted on the phenyl with 1, 2 or 3 C₁-C₄ alkyls,or an aliphatic C₁-C₈ acyl; R² is hydrogen, C₁-C₈ alkyl, or benzyl; R³,R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, ortwo geminal R moieties, which together with the carbon to which they areattached form a C₅-C₁₀ cycloalkyl; and A is either ZR or a hydrocarbylgroup.

[0020] In one embodiment R¹ is a H, C₁-C₄ alkyl, O, OH; C₁-C₁₈ alkoxy,C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy or C₅-C₁₂ hydroxycycloalkoxy,R² is H, or C₁-C₄ alkyl; R³, R⁴, R⁵, and R⁶ are each H or C₁-C₄ alkyl;R^(a), R^(b), R^(c), and R^(d), are each a hydrogen, aromatic, or C₁-C₄alkyl; and n is from 4 to 11. In another embodiment R¹ is H or CH₃; R³,R⁴, R⁵, and R⁶ are each CH₃; R² is hydrogen; R^(a), R^(b), R^(c) andR^(d) are each a hydrogen; Z is —O—; m is 0 or 1; and n is and integerfrom 4 to 10.

[0021] The invention also provides a method of forming the HALS of theinvention. The HALS of the invention may be prepared by combining one ormore multi-functional carbonyl compounds of general structure:

DO—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)—NH—(Y)_(m)—CO—B

[0022] wherein n is an integer from 1 to 15, in is either 0 or 1; R^(a),R^(b), R^(c), and R^(d), are each a hydrogen or a hydrocarbyl group; Yis CO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f) are each a hydrogen orhydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C₆H₄—,wherein the substitution pattern on the phenylene group is an ortho,meta, or para substitution pattern and wherein one or more of thehydrogens of the phenylene group may be substituted by a hydrocarbylgroup or a functional group; D is a hydrocarbyl group; and B is eitherOD or D; with one or more 1-substituted piperidin-4-ol or4-aminopiperidines of general structure

[0023] wherein Z is OH or NHG, wherein G is as defined above; R¹ ishydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈hydroxyalkoxy, C₁-C₁₂ cycloalkoxy, C₁-C₁₂ hydroxycycloalkoxy, C₃-C₆alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted or substitutedon the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl;R² represents hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ areeach a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal Rmoieties, which together with the carbon to which they are attached forma C₅-C₁₀ cycloalkyl, to form a reaction mixture; reacting the reactionmixture for a sufficient time to form the compound of formula (I); andrecovering the compound of formula (I) from the reaction mixture.

[0024] The one or more multifunctional carbonyl compounds may be presentin an amount of about 0.025 to 2.5 M and the molar ratio of the one ormore multi-functional carbonyl compounds to the one or more1-substituted piperidin-4-ol or 4-aminopiperidines may be from about20:1 to 1:5. The 4-piperidin-4-ol may be1,2,2,6,6-pentamethyl-4-piperidinol or 2,2,6,6-tetramethyl-4-piperidinoland the multi-functional carbonyl compound may be methyl6-(methoxycarbonylamino)hexanoate, butyl 6-(butoxycarbonylamino)undecanoate, methyl 6-(butoxycarbonylamino)undecanoate, butyl6-(methoxycarbonylamino)undecanoate, methyl6-(methoxycarbonylamino)undecanoate, and combinations thereof.

[0025] The reaction mixture may include a solvent. The solvent may beone or more of benzene, toluene, or one or more xylenes. The reactionmixture may also include a catalyst. The catalyst may be a base catalystor an acid catalyst. The base catalyst may be methoxide. The acidcatalyst may be a Lewis acid. The Lewis acid may be aluminumtrichloride, aluminum tribromide, trimethylaluminum, boron trifluoride,boron trichloride, 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane, zincdichloride, titanium tetrachloride, titanium (IV) isopropoxide, tindichloride, tin tetrachloride, a tetraalkoxytitanate, and mixturesthereof. The catalyst may be present in an amount of less than about 30mole percent based on the molar quantity of the multi-functionalcarbonyl compound.

[0026] In another embodiment the HALS of the invention are prepared froma lactam in a single-step by combining one or more lactams of generalstructure:

[0027] wherein n is an integer from 1 to 15 and R^(a), R^(b), R^(c), andR^(d) are each a hydrogen or a hydrocarbyl group with one or morecarbonyl compounds of general structure

[0028] wherein m is either 0 or 1, D is a hydrocarbyl group and B is ahydrocarbyl group or OD and Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) andR^(f) are each a hydrogen or hydrocarbyl group and p is zero or aninteger from 1 to 20 or CO—C₆H₄—, and the substitution pattern on thephenylene group may be an ortho, meta, or para substitution pattern, andone or more of the hydrogens of the phenylene group may be substitutedby a hydrocarbyl group or other functional group; and one or more1-substituted piperidin-4-ol or 4-aminopiperidines of general structure

[0029] wherein Z is OH or NHG, wherein G is as defined above; R¹ ishydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy, C₃-C₆alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted or substitutedon the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl;R² represents hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ areeach a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal Rmoieties, which together with the carbon to which they are attached,form a C₅-C₁₀ cycloalkyl to provide a reaction mixture; reacting thereaction mixture for a sufficient time to form the compound of formula(I); and recovering the compound of formula (I) from the reactionmixture.

[0030] The carbonyl compound may be a dialkyl carbonate, a dialkyloxalate, a dialkyl diester, an alkyl ester, or a mixtures thereof.

[0031] The reaction mixture may include a catalyst. The catalyst may bea base catalyst or an acid catalyst. The base catalyst may be methoxide.The acid catalyst may be a Lewis acid. The Lewis acid may be aluminumtrichloride, aluminum tribromide, trimethylaluminum, boron trifluoride,boron trichloride, 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane, zincdichloride, titanium tetrachloride, titanium (IV) isopropoxide, tindichloride, tin tetrachloride, a tetraalkoxytitanate, and mixturesthereof. The reaction mixture may also include a solvent. The solventmay be one or more of benzene, toluene, or one or more xylenes.

[0032] The concentration of lactam may be from about 0.025 to 10 M. Theratio of lactam to carbonyl compound may be from about 2:1 to 1:4; theratio of lactam to 1-substituted piperidin-4-ol or 4-aminopiperidine maybe from about 1:1; to 1:6; and the catalyst may be present in an amountof less than about 30 mole percent relative to the amount of carbonylcompound.

[0033] In one embodiment n is from 3 to 12 and the catalyst is a basecatalyst or a Lewis acid. In another embodiment the lactam comprisescaprolactam or laurolactam.

[0034] The invention also provides for a method of forming amulti-functional carbonyl compound having the structure:

DO—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH— (Y)_(m)—CO—B

[0035] wherein n is an integer from about 1 to 15, m is either 0 or I;R^(a), R^(b), R^(c), and R^(d) are each a hydrogen or a hydrocarbylgroup; Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f) are each ahydrogen or hydrocarbyl group and p is an integer from about 0 to 20,preferably 0 to 10, or CO—C₆H₄—, wherein the substitution pattern on thephenylene group is an ortho, meta, or para substitution pattern and oneor more of the hydrogens of the phenylene group may be substituted by ahydrocarbyl group or a functional group; D is a hydrocarbyl group; and Bis either OD or D. The method involves combining one or more lactams ofgeneral structure

[0036] wherein n and R^(a), R^(b), R^(c), and R^(d) are as defined abovewith one or more carbonyl compounds of general structure

[0037] wherein D, B, Y, and m are as defined above; and a Lewis acidcatalyst to provide a reaction mixture; reacting the reaction mixturefor a sufficient time to produce the multi-functional carbonyl compound;and recovering the multi-functional carbonyl compound from the reactionmixture.

[0038] In one embodiment n is from about 3 to 12. The Lewis acidcatalyst may be aluminum trichloride, aluminum tribromide,trimethylaluminum, boron trifluoride, boron trichloride, zincdichloride, titanium tetrachloride, titanium (IV) isopropoxide, tindichloride, tin tetrachloride, a tetraalkoxytitanate, and mixturesthereof. The reaction mixture may also include a solvent. The solventmay be one or more of benzene, toluene, or one or more xylenes.

[0039] The concentration of the one or more lactams may be from about0.075 M to 10 M. The mole ratio of the one or more lactams to the one ormore carbonyl compounds may be from about 1:10 to 5:1. The catalyst maybe present in an amount of less than about 30 mole percent relative tothe amount of carbonyl compound. The lactam may be caprolactam orlaurolactam.

[0040] Another method for forming the multi-functional carbonyl compoundinvolves combining one or more lactams of general structure

[0041] wherein n, R^(a), R^(b), R^(c), and R^(d) are as defined abovewith one or more carbonyl compounds of general structure

[0042] wherein D, B, Y, and m are as defined above; and a basic catalystto provide a reaction mixture; reacting the reaction mixture at atemperature less than about 20° C. for a sufficient time to produce themulti-functional carbonyl compound; and recovering the multi-functionalcarbonyl compound from the reaction mixture. The temperature may lessthan about 15° C. The reaction may be conducted in a solvent. The basecatalyst may be methoxide.

DETAILED DESCRIPTION OF THE INVENTION

[0043] An improved class of HALS compounds has now been discovered thatprovides substantially similar or superior UV light protection over alonger period of time compared to conventional HALS compounds. The HALScompounds of the present invention are based on the reaction of a lactamwith the carbonyl group of a carbonyl compound. The HALS compounds ofthe present invention include compounds where the functional componentof the HALS compound, a piperidin-4-ol or 4 aminopiperidine group, isanchored to the terminus of a hydrocarbon chain by an esterfunctionality or an amide functionality and wherein the other end of thehydrocarbon chain terminates with an amide linkage that is not a HALSfunctionality. These may be referred to as “ester/amide HALS compounds”and “amide/amide HALS compounds.” Alternatively, both ends of thehydrocarbon chain can terminate with the piperidin-4-ol or 4aminopiperidine group. In this embodiment, the HALS molecule is anchoredto one terminus of the hydrocarbon chain by an ester functionality andto the other terminus by a urethane functionality. These may be referredto as “ester/urethane HALS compounds.” Furthermore, the HALS moleculemay be anchored to one terminus of the hydrocarbon chain by an amidefunctionality and to the other terminus by a urea functionality. Thesemay be referred to as “amide/urea HALS compounds.” In yet another seriesof compounds, the piperidin-4-ol or 4 aminopiperidine group is bonded byan ester linkage to one terminus of the hydrocarbon chain and by anoxamate linkage at the other terminus of the hydrocarbon chain toprovide “ester/oxamate HALS compounds,” or the piperidin-4-ol or 4aminopiperidine group is bonded by an amide linkage to one terminus ofthe hydrocarbon chain and by an oxamide linkage at the other terminus ofthe hydrocarbon chain to provide “amide/oxamide HALS compounds.”

Monomeric HALS Compounds of the Invention

[0044] These HALS compounds are represented by the general formula (I)

RZ—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH—(Y)_(m)—CO—A  (I)

[0045] wherein n is an integer from 1 to 15, preferably 4 to 1; m iseither 0 or 1; R^(a), R^(b), R^(c), and R^(d), are each a hydrogen or ahydrocarbyl group; Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f)are each a hydrogen or hydrocarbyl group and p is zero or an integerfrom 1 to 20 or CO—C₆H₄—, and the substitution pattern on the phenylenegroup, i.e., —C₆H₄—, may be an ortho, meta, or para substitutionpattern, in addition one or more of the hydrogens of the phenylene groupmay be substituted by a hydrocarbyl group or other functional groupcommonly found in organic molecules; Z is —O— or NG, wherein G is H,C₁-C₁₂ alkyl or the radical R; wherein the radical R represents:

[0046] wherein R¹ is hydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈alkoxy, C₁-C₁₈ hydroxyalkoxy, C₁-C₁₂ cycloalkoxy, C₅-C₁₂hydroxycycloalkoxy, C₃-C₆ alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl,unsubstituted or substituted on the phenyl with 1, 2 or 3 C₁-C₄ alkyls,or an aliphatic C₁-C₈ acyl; R² is hydrogen, C₁-C₈ alkyl, or benzyl; R³,R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, ortwo geminal R moieties, which together with the carbon to which they areattached, form a C₅-C₁₀ cycloalkyl; and A is either ZR or a hydrocarbylgroup.

[0047] The term “hydrocarbyl,” as used herein, is a monovalenthydrocarbon group in which the valency is derived by extraction of ahydrogen from a carbon. Hydrocarbyl includes, for example, aliphatics(straight and branched chain), cycloaliphatics, aromatics and mixedcharacter groups (e.g., aralkyl and alkaryl). Hydrocarbyl also includesgroups with internal unsaturation and activated unsaturation. Morespecifically, hydrocarbyl includes, but is not limited to, alkyl,cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl, and alkynyl,typically having from about 1 to 24 carbon atoms, preferably having fromabout 1 to 12 carbon atoms. A hydrocarbyl may contain one or morecarbonyl groups (which is/are included in the carbon count) and/or aheteroatom or heteroatoms (such as at least one oxygen, nitrogen,sulfur, or silicon) in the chain or ring. In addition, a hydrocarbyl mayhave one or more of the hydrogens of the hydrocarbon group replaced by afunctional group commonly found in organic molecules. The phrase“functional group commonly found in organic molecules” meansnon-hydrocarbyl groups that are typically found in organic moleculesincluding, but not limited to, halides, cyano groups, amino groups,thiol groups, carboxylate groups, hydroxyl groups, sulfonate groups,nitroso groups, nitro groups, and the like.

[0048] The term “hydrocarbylene” in the context of the present inventionis a divalent hydrocarbon group in which both valencies derive byabstraction of hydrogens from carbon atoms. Included within thedefinition of hydrocarbylene are the same groups as indicated above forhydrocarbyl and functional hydrocarbyl with, of course, the extravalency (for example, alkylene, alkenylene, arylene, etc.).

[0049] In a preferred embodiment of the invention, R¹ is H, C₁-C₄ alkyl,C₁-C₈ alkoxy, C₁-C₁₂ cycloalkoxy, O, or OH; R₂ is H, or C₁-C₄ alkyl;R³, R⁴, R⁵, and R⁶ are H or C₁-C₄ alkyl; R^(a), R^(b), R^(c), and R^(d),are each a hydrogen, aromatic, or C₁-C₄ alkyl; and n is from about 2 to10. In a more preferred embodiment, R represents the2,2,6,6-tetramethylpiperidine radical (i.e., R³, R⁴, R⁵, R⁶ are methyland R² is hydrogen) or 1,2,2,6,6-pentamethylpiperidine radical (i.e.,R², R³, R⁴, R⁵, and R⁶ are methyl); R^(a), R^(b), R^(c), and R^(d) areeach a hydrogen; Z is —O—; m is 0 or 1; and n is 4 to 10.

Synthesis of Monomeric HALS Compounds

[0050] The HALS compounds of the formula (I) are typically prepared bythe reaction of a multi-functional carbonyl compound with a4-piperidin-ol or a 4-aminopiperidine moiety. The multi-functionalcarbonyl compound has the general structure:

DO—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH—(Y)_(m)—CO—B

[0051] wherein n is an integer from 1 to 15, preferably 4 to 11; m iseither 0 or 1; R^(a), R^(b), R^(c) and R^(d), are each a hydrogen or ahydrocarbyl group; Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f)are each a hydrogen or hydrocarbyl group, and p is zero or an integerfrom about 1 to 20 or CO—C₆H₄—, and the substitution pattern on thephenylene group, i.e., —C₆H₄—, is an ortho, meta, or para substitutionpattern, in addition one or more of the hydrogens of the phenylene groupmay be substituted by a hydrocarbyl group or a functional group commonlyfound in organic molecules; D is a hydrocarbyl group; and B is either ODor D; and reacting the carbonyl compound with a 1-substitutedpiperidin-4-ol or 4-aminopiperidine of general structure:

[0052] wherein Z is OH or NHG, wherein G is H or C₁-C₁₂ alkyl or theradical R (wherein R is defined above); and R¹ is hydrogen, C₁-C₁₈alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂cycloalkoxy, C₁-C₁₂ hydroxycycloalkoxy, C₃-C₆ alkenyl, C₁-C₁₈ alkynyl,C₇-C₉ phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl; R² is hydrogen, C₁-C₈alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₈ alkyl,benzyl or phenethyl, or two geminal R moieties, which together with thecarbon to which they are attached, to form a C₅-C₁₀ cycloalkyl.

[0053] The reaction between the multi-functional carbonyl compound andthe 4-piperidin-ol or 4-aminopiperidine moiety is conducted for asufficient time for the compound of formula (I) to be formed. The phrase“conducted for a sufficient time for the compound of [a given formula]to be formed” means that after the reactants are combined they areallowed to react for sufficient time to produce a detectable amount ofthe desired compound, i.e., the compound of a given formula. By“detectable amount” of a compound is meant an amount of the compoundthat can be detected by any means readily available to those of ordinaryskill in the art. Means for detecting the formation of a compound in areaction mixture include, but are not limited to, thin layerchromatography (TLC), high performance liquid chromatography (HPLC), gaschromatography (GC), column chromatography, nuclear magnetic resonancespectroscopy (NMR), infra-red (IR) spectroscopy, ultra-violet (UV) orvisible (VIS) spectroscopy, and wet-chemical analysis, for example. Thelength of time for the desired compound to be produced is dependent on anumber of variables and, thus, cannot be generalized. For example, thereaction time is dependent on the temperature, the pressure, thespecific reactants (i.e., the multi-functional carbonyl compound and the1-substituted piperidin-4-ol or 4-aminopiperidine), and the solvent andcatalyst, if present. Acceptable parameters that produce the desiredproduct, however, may be readily determined by those of ordinary skillin the art without undue experimentation.

[0054] The reaction may be carried out in the absence of a solvent or inthe presence of a solvent. When the reaction is carried out in theabsence of a solvent either the multi-functional carbonyl compound orthe 4-piperidin-ol or 4-aminopiperidine may be present in an excess andemployed as the reaction medium. Alternatively, the multi-functionalcarbonyl compound and 4-piperidin-ol or 4-aminopiperidine can be presentin a stoichiometric amount. The multi-functional carbonyl compound and4-piperidin-ol or 4-aminopiperidine may be present in a melt.Preferably, the reaction is carried out in an organic solvent. Anysolvent compatible with the reagents may be used. Preferred solvents foruse in the method of the invention include, but are not limited to,hydrocarbon solvents such as a saturated alkanes; benzene; toluene;xylenes; halogenated hydrocarbons; ethers such as ethyl ether; cyclicethers such as tetrahydrofuran and dioxane; amides such asdimethylformamide; sulfoxides such as dimethylsulfoxide; ketones such as2-butanone or methyl isobutyl ketone; and the like; or combinationsthereof. The more preferred solvents include toluene, benzene, andxylenes.

[0055] When the reaction is carried out in a solvent the concentrationof the multi-functional carbonyl in the organic solvent is generallyfrom about 0.025 M to 2.5 M, preferably from about 0.125 M to 2 M, andmore preferably from about 0.25 M to 1.35 M. The molar ratio of the1-substituted piperidin-4-ol or 4-aminopiperidine to themulti-functional carbonyl compound is between about 20:1 and 1:5,preferably between about 10:1 and 1:3, and more preferably between about5:1 and 1:5.

[0056] The reaction of the multi-functional carbonyl compound and4-piperidin-ol or 4-aminopiperidine produces an alcohol of structureDOH. Preferably, the alcohol is removed from the reaction mixture as itis formed to help drive the reaction to completion. The alcohol may beremoved by any means available to those of ordinary skill in the artsuch as distillation and or azeotropic distillation.

[0057] Preferably, the reaction is conducted in the presence of acatalyst. The optional catalyst may be a basic or an acidic catalyst.The phrase “base catalyst” means any compound that can abstract aproton. Base catalysts suitable for the invention include, but are notlimited to, alkoxide ions; hydroxide ion; amide ion; and amines such astriethylamine, DBU (1,8-diazabicyclo[5.4.0] undec-7-ene), or DBN(1,5-diazabicyclo [4.3.0] non-5-ene). When an amine is used as the base,it is preferred that the amine is a tertiary amine.

[0058] The phrase “acid catalyst” means any inorganic or organic acidwith at least one acidic proton or a Lewis acid. The organic acidsinclude any organic compound that contains at least one acidicfunctional group, including one or more of RCO₂H, RSO₃H, RSO₂H, RSH,ROH, RPO₃H, RPO₂H, wherein R is a hydrocarbyl group. Preferred proticacids include HCl, HBr, HI, HNO₃, HNO₂, H₂S, H₂SO₄, H₃PO₄, H₂CO₃, aceticacid, formic acid, propionic acid, butanoic acid, benzoic acid, phthalicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, methanesulfonic acid, and p-toluenesulfonic acid, or mixturesthereof. Lewis acids suitable for the method of the invention include,but are not limited to, aluminum halides, alkylaluminum halides, boronhalides, dialkyl tin oxides and derivatives thereof, tin halides,titanium halides, lead halides, zinc halides, iron halides, galliumhalides, arsenic halide, copper halides, cadmium halides, mercuryhalides, antimony halides, and the like. Preferred Lewis acids includealuminum trichloride, aluminum tribromide,1,3,-diacetoxy-1,1,3,3-tetrabutyldistannoxane, trimethylaluminum, borontrifluoride, boron trichloride, zinc dichloride, titanium tetrachloride,titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, atetraalkoxytitanate or a mixture thereof.

[0059] The acid or base catalyst may also be a solid supported catalystsuch as amberlyst catalysts.

[0060] The catalyst is typically added in an amount of less than about30 mole percent based on the molar quantity of the multi-functionalcarbonyl compound, preferably less than about 20 mole percent based onthe molar quantity of the multi-functional carbonyl compound, morepreferably less than about 10 mole percent based on the molar quantityof the multi-functional carbonyl compound, and most preferably less thanabout 5 mole percent by weight based on the weight of themulti-functional carbonyl compound.

[0061] The preferred base catalyst for use in the method of theinvention is methoxide ion. The preferred acid catalyst is a Lewis acid.The preferred Lewis acid is1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane.

[0062] Preferably, the reaction is allowed to proceed for a time that isless than about 20 hours and more preferably less than about 10 hours.Typically, the reaction temperature is from about room temperature to150° C., for example, up to the boiling point of the solvent. Typically,the reactions are run at atmospheric pressure. Representative reactionconditions for forming the compound of formula (I) are provided in theexamples.

[0063] After the compound of formula (I) is formed, it is recovered fromthe reaction mixture by any means available to those of ordinary skillin the art. Methods for recovering compounds from a reaction mixtureinclude, but are not limited to, chromatography, recrystallization,distillation, extraction, and the like. More than one method may be usedto recover a compound from the reaction mixture.

[0064] In a preferred embodiment, the substituted 4-piperidin-4-ol is1,2,2,6,6-pentamethyl-4-piperidinol or 2,2,6,6-tetramethyl-4-piperidinoland the multi-functional carbonyl compound is methyl6-(methoxycarbonylamino)hexanoate, butyl 6-(butoxycarbonylamino)undecanoate, methyl 6-(butoxycarbonylamino)undecanoate, butyl6-(methoxycarbonylamino)undecanoate, or methyl6-(methoxycarbonylamino)undecanoate.

[0065] The multi-functional carbonyl compounds can be prepared by anymethod available to those of ordinary skill in the art. In oneembodiment, the multi-functional carbonyl compound is prepared byreacting a lactam with a carbonyl compound. For example, themulti-functional carbonyl compound can be prepared by the base catalyzedreaction of a lactam and a carbonyl compound according to the methoddisclosed in U.S. Pat. No. 5,300,678, the contents of which areexpressly incorporated herein by reference thereto.

[0066] Any lactam may be used according to the method of the invention.Preferably the size of the lactam ring is from about 4 to 13 atoms. Morepreferably the lactam is caprolactam or laurolactam.

[0067] The carbonyl compound must include at least one reactive carbonylgroup. “Reactive carbonyl group” means any carbonyl group that isattached to a good leaving group and, thus, is activated towardsnucleophilic acyl substitution. The reactive carbonyl group may be, forexample, an ester or acid chloride. Preferably the carbonyl compound isan ester. More preferred carbonyl compounds include dialkyl carbonates,dialkyl oxalates, dialkyl diesters, or alkyl esters. The generalstructure of the carbonyl compound is

[0068] wherein m is either 0 or 1, Q is a good leaving group, such aschloride or OD, wherein D is a hydrocarbyl group, preferably methyl, andB is Q or a hydrocarbyl group and Y is CO—(CR^(e)R^(f))_(p), whereinR^(e) and R^(f) are each a hydrogen or hydrocarbyl group and p is zeroor an integer from about 1 to 20 or CO—C₆H₄—, and the substitutionpattern on the phenylene group, i.e., —C₆H₄—, may be an ortho, meta, orpara substitution pattern, in addition one or more of the hydrogens ofthe phenylene group may be substituted by a hydrocarbyl group or otherfunctional group commonly found in organic molecules.

[0069] When the carbonyl compound is a dialkyl carbonate, the resultingmulti-functional carbonyl compound is a hydrocarbon chain thatterminates on one end with an ester functionality and the other end witha urethane functionality. When the carbonyl compound is a dialkyloxalate, the resulting multi-functional carbonyl compound is ahydrocarbon chain that terminates on one end with an ester functionalityand the other end with an oxamate functionality. When the carbonylcompound is a dialkyl ester, the resulting multi-functional carbonylcompound is a hydrocarbon chain that includes an amide linkage andterminates on each end with an ester functionality. When the carbonylcompound is an alkyl ester, the resulting multi-functional carbonylcompound is a hydrocarbon chain that terminates on one end with an esterfunctionality and the other end with an amide functionality.

[0070] The reaction of the lactam with the carbonyl compound can beconducted in a solvent or in the absence of a solvent. When the reactionis conducted in the absence of a solvent, excess carbonyl compound maybe employed as the reaction medium and, thus, the carbonyl compound maybe present in an excess compared to the lactam. The lactam, however, mayalso be present in an excess and employed as the reaction medium.Alternatively, the lactam and carbonyl compound can be present in astoichiometric amount. The lactam and carbonyl compound may be presentin a melt. When the reaction is conducted in the absence of a solvent,the excess carbonyl compound or lactam may be recovered by, for example,distillation and reused. An advantage of not using a solvent is that theproblems associated with disposal of waste solvents are avoided.

[0071] In another embodiment one or more different lactams are reactedwith one or more different carbonyl compounds. For example, two lactammolecules can be reacted with 1 molecule of carbonyl compound.

[0072] Solvents suitable for the method of the invention include, butare not limited to, hydrocarbon solvents such as a saturated alkane;benzene; toluene; xylenes; halogenated hydrocarbons; ethers such asethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; amidessuch as dimethylformamide; sulfoxides such as dimethylsulfoxide; ketonessuch as 2-butanone or methyl isobutyl ketone; alcohols; and the like; ormixtures thereof. When the reaction is carried out in a solvent theconcentration of the lactam in the solvent is from about 0.025 M to 10M, preferably from about 0.375 M to 6 M, and more preferably from about0.25 M to 4 M. The mole ratio of lactam to carbonyl compound istypically from about 1:10 to 5:1, preferably from about 1:5 to 2:1, andmore preferably from about 1:2.5 to 1.5:1.

[0073] The reaction is allowed to proceed for a sufficient time to forma detectable amount of the multi-functional carbonyl compound. Ingeneral the reaction time is less than about 12 hours. Typically, thereaction temperature is from about room temperature to 150° C., forexample, up to the boiling point of the solvent, when a solvent is used.The reaction is typically conducted at room temperature.

[0074] The present invention also provides an improved method forpreparing the multi-functional carbonyl compound. According to themethod of the invention the lactam and a carbonyl compound are reactedin the presence of an acid catalyst, preferably a Lewis acid catalyst.

[0075] Any Lewis acid catalyst can be used according to the method ofthe invention. For example, any of the above-mentioned Lewis acidcatalysts may be used. Preferably the Lewis acid catalyst is titanium(IV) isopropoxide. Lewis acids are a preferred catalyst since they canbe easily removed from the reaction mixture. For example, many Lewisacids, such as tetraorganotitanates, can be readily hydrolyzed with astoichometric amount of water, leading to a highly insoluble titaniumdioxide that can easily be removed from the reaction mixture byfiltration. Other Lewis acids, such as, for example, boron trifluorideetherate, are sufficiently volatile that they can easily be removed fromthe reaction mixture by distillation. Thus, using a Lewis acid canadvantageously avoid having to extract the reaction mixture with anaqueous solvent to remove the catalyst. By avoiding an extraction stepto remove the catalyst, the method of the invention generates lessaqueous waste that ultimately has to be disposed of.

[0076] In another improved method of the invention, the lactam andcarbonyl compound are allowed to react with an alkoxide anion as a basiccatalyst, preferably methoxide anion. The reaction, however, isconducted at a temperature of less than about 20° C., preferably lessthan about 19° C., and more preferably less than about 15° C. The lactamand carbonyl compound are allowed to react for less than about 5 hours,preferably less than about 2 hours, and more preferably less than about1 hour. Conducting the reaction at a low temperature is preferred sincetemperatures can be kept below the flash point of many reagents and,thus, such low temperature reactions can be significantly safer. Forexample, dimethyl carbonate (which is a common carbonyl compound for usein the method of the invention) has a flash point of 19° C. By runningthe reaction at a temperature below 19° C., i.e., below the flash point,the method is significantly safer than prior art methods that requirehigher temperatures.

[0077] When the multi-functional carbonyl compound is formed, it can berecovered from the reaction mixture before it is reacted with the1-substituted piperidin-4-ol or 4-aminopiperidine to form the HALS ofthe invention. The multi-functional carbonyl compound may be recoveredby any means available to those of ordinary skill in the art.Optionally, the multi-functional carbonyl compound is not recovered fromthe reaction mixture and instead the 1-substituted piperidin-4-ol or4-aminopiperidine is added to the reaction mixture after a detectableamount of the multi-functional carbonyl compound is formed. The1-substituted piperidin-4-ol or 4-aminopiperidine and themulti-functional carbonyl compound can then react to form the HALS ofthe invention.

[0078] In a preferred method, the compound of formula (I) is prepared byreacting the lactam, carbonyl compound, and 1-substituted piperidin-4-olor 4-aminopiperidine in a single step. The lactam, the carbonylcompound, and the 1-substituted piperidin-4-ol or 4-aminopiperidine arecombined and allowed to react at the same time, rather than reacting thelactam and carbonyl compound to form the multi-functional carbonylcompound in a first step and then, in a subsequent step, reacting themulti-functional carbonyl compound with the 1-substituted piperidin-4-olor 4-aminopiperidine. The lactam, the carbonyl compound, and the1-substituted piperidin-4-ol or 4-aminopiperidine are combined in areaction vessel and allowed to react for sufficient time to form adetectable amount of the HALS of formula (I).

[0079] The ratio of lactam to carbonyl compound in this embodiment ofthe method is from about 2:1 to 1:4, preferably from about 1:1 to 1:2;and the ratio of lactam to 1-substituted piperidin-4-ol or4-aminopiperidine is from about 1:1 to 1:6, preferably from about 1:2 to1:4.

[0080] The single step reaction can be conducted in a solvent or in theabsence of a solvent. When a solvent is used, any solvent that iscompatible with the reagents may be used. Representative solventsinclude, but are not limited to, those solvents described above for thereaction of a 1-substituted piperidin-4-ol or 4-aminopiperidine with amulti-functional carbonyl compound. Preferably, the reaction in thisembodiment is carried out in the presence of a solvent. When a solventis employed, the concentration of lactam is typically from about 0.025 Mto 10 M, preferably from about 0.325 M to 6 M, and more preferably fromabout 0.75 M to 4 M.

[0081] Preferably, the reaction is carried out in the presence of acatalyst. The same catalysts may be used as were used in the reaction ofa 1-substituted piperidin-4-ol or 4-aminopiperidine with amulti-functional carbonyl compound. The catalyst is typically present inan amount of less than about 30 mole percent, preferably less than about20 mole percent, and more preferably less than about 10 mole percent,and most preferably less than 5 mole percent, relative to the amount ofcarbonyl compound.

[0082] Preferably, the carbonyl compound is an ester, i.e., Q=OD, sothat the reaction produces an alcohol of structure HOD. Preferably, thealcohol is removed from the reaction mixture as it is formed to drivethe reaction to completion. The alcohol may be removed by any meansavailable to those of ordinary skill in the art, such as distillationand/or azeotropic distillation.

[0083] Preferably, the reaction time is less than about 20 hours andmore preferably less than about 10 hours. Typically, the reactiontemperature is between about room temperature and 250° C. Typically, thereactions are run at atmospheric pressure. Representative reactionconditions for forming the HALS of formula (I) by the single stepprocess are provided in the examples. When the HALS of formula (I) isformed it may be recovered from the reaction mixture by any meansavailable to those of ordinary skill in the art.

Oligomeric HALS Compounds of the Invention

[0084] The invention also includes oligomeric HALS having the generalformula (II)

T-E-F_(i)E-F′_(j)E′-F_(k)E′-F′_(l)-S  (II)

[0085] wherein i, j, k, and l are integers from about 0 to 300,preferably about 0 to 200, and more preferably 0 to about 100. The sumof i, j, k, and l is greater than 2, preferably, the sum of i, j, k, andl is greater than about 3 and more preferably is greater than about 6.Preferably at least two of i, j, k, and l or more, or (III)

T-M-F_(i)M-F′_(j)-M  (III)

[0086] wherein i and j are integers from about 0 to 300, preferablyabout 0 to 200, and more preferably 0 to about 100. The sum of i and jis greater than 2. Preferably, the sum of i and j is greater than about3, more preferably greater than about 6. Preferably at least two of i,j, k, and l are equal to or greater than 1.

[0087] In formula (II) E and E′ are a piperidin-4-ol or4-aminopiperidine moiety and F and F′ are each a multi-functionalcarbonyl compound. T can be F, F′, or hydrogen and S can be E, E′, orhydrogen.

[0088] E-F includes:

[0089] E-F′ includes:

[0090] E′-F includes:

[0091] and E′-F′ includes:

[0092] In formula (III), M is a diamino or a dihydroxy group thatcontains the 4-aminopiperidine group, R, as defined above. By “diaminoor a dihydroxy group” is meant a group derived from a compound thatcontains at least two hydroxy groups, at least two amino groups, or atleast one amino group and one hydroxy group. The amino group can beeither a primary or secondary amino group.

[0093] M-F includes:

[0094] M-F′ includes:

[0095] In the oligomeric HALS of formula (III) the diamino or dihydroxygroup that contains the 4-aminopiperidine group, i.e., M, is bonded tothe multi-functional carbonyl compound by the hydroxy or amino group.

[0096] Formulas II and III may be a block copolymer or a randomcopolymer, i.e., the units E-F, E-F′, E′-F, and E′-F′ or M-F and M-F′are distributed randomly throughout the polymer chain. In the aboveoligomeric HALS of structure (II) or (III) S is a hydrogen, or a unitderived from a piperidin-4-ol or a 4-aminopiperidine moiety and has thestructure

[0097] and T is a hydrogen or a unit derived from a multi-functionalcarbonyl compound and has the structure

[0098] wherein D is a hydrocarbyl group.

[0099] In the oligomeric HALS of formula (II) and (III) n is an integerfrom 1 to 15, preferably 4 to 11, m is either 0 or 1, s is 0 or aninteger from about 1 to 10; R^(a), R^(b), R^(c), and R^(d), are each ahydrogen or a hydrocarbyl group; Y is CO—(CR^(e)R^(f))_(p), whereinR^(e) and R^(f) are each a hydrogen or hydrocarbyl group and p is zeroor an integer from about 1 to 20 or CO—C₆H₄—, wherein the substitutionpattern on the phenylene group is an ortho, meta, or para substitutionpattern, and one or more of the hydrogens of the phenylene group may besubstituted by a hydrocarbyl group or a functional group commonly foundin organic molecules; Z is —O— or NG, wherein G is H or C₁-C₁₂ alkyl; R²is hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ are each ahydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal R moieties,which together with the carbon to which they are attached, form aC₅-C₁₀cycloalkyl; and when s is greater than 0, P is NH or O; and when sis 0, P=O or O—L—O, where L is a hydrocarbylene.

[0100] As noted above, in the HALS of formula (II), E, E′ and S areunits derived from a piperidin-4-ol or a 4-aminopiperidine moiety and F,F′ and T are units derived from a multi-functional carbonyl compound andin the HALS of formula (III) F and F′ are derived from amulti-functional carbonyl compound and M is as defined above. In theHALS of formula (II) it is preferably that the mole percent of the unitsderived from the multi-functional carbonyl compound is greater than themole percent of the units derived from a piperidin-4-ol or a4-aminopiperidine moiety. In the HALS of formula (III) it is preferablythat the mole percent of the units derived from the multi-functionalcarbonyl compound is greater than the mole percent of the diamino ordihydroxy group that contains the 4-aminopiperidine group, i.e., M. Thisis advantageous since they are less expensive.

[0101] Preferably, in the oligomeric HALS of formula (II), R² is H, orC₁-C₄ alkyl; R³, R⁴, R⁵, and R⁶ are each H or C₁-C₄ alkyl; R^(a), R^(b),R^(c), and R^(d), are each a hydrogen, aromatic, or C₁-C₄ alkyl; n isfrom about 4 to 11; and s is from about 2 to 5. In a more preferredembodiment, R² is a hydrogen; R³, R⁴, R⁵, and R⁶ are each methyl; R^(a),R^(b), R^(c), and R^(d), are each a hydrogen, Z is 0, n is between 4 and11, and s is 2, m is 0 and P is O.

[0102] In another embodiment, R² is hydrogen, R³, R⁴, R⁵ and R⁶ aremethyl, R^(a), R^(b), R^(c) and R^(d) are each hydrogen, Z is O, n isfrom 4 to 11 and s is 0.

[0103] Preferably, in the oligomeric HALS of formula (III), M isN,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine (BPIP) orN-(2,2,6,6-tetramethylpiperidinol) diethanolamine and n is from about 4to 11.

[0104] Advantageously, the number average molecular weight of theoligomeric HALS compound of formula (II) and (III) is typically fromabout 400 to 20,000, preferably, from about 1,000 to 15,000, and morepreferably from about 2,000 to 9,000.

Synthesis of Oligomeric HALS Compounds

[0105] The present invention also relates to a method of formingoligomeric HALS of formula (II) and formula (III). Oligomeric HALS offormula (II) are prepared by reacting a multi-functional carbonylcompound of general structure

DO—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH—(Y)_(m)—CO—OD  (IV)

[0106] wherein n is an integer from about 1 to 15, preferably 4 to 11, mis either 0 or 1; R^(a), R^(b), R^(c), and R^(d), are each a hydrogen ora hydrocarbyl group; Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f)are each a hydrogen or hydrocarbyl group and p is zero or an integerfrom about 1 to 20 or CO—C₆H₄—, wherein the substitution pattern on thephenylene group may be an ortho, meta, or para substitution pattern, andone or more of the hydrogens of the phenylene group may be substitutedby a hydrocarbyl group or a functional group commonly found in organicmolecules; and D is a hydrocarbyl group, with a 1-substitutedpiperidin-4-ol or 4-aminopiperidine of general structure:

[0107] wherein Z is OH or or NHG, wherein G is H or C₁-C₁₂ alkyl; R¹ is—(CH₂)_(s)—OH, —(CH₂)_(s)—NH₂, C₁-C₁₈ hydroxyalkoxy or C₅-C₁₂hydroxycycloalkoxy; wherein s is an integer from about 1 to 10,preferably 2 to 8; R² represents hydrogen, C₁-C₈ alkyl, or benzyl; R³,R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, ortwo geminal R moieties, which together with the carbon to which they areattached, form a C₅-C₁₀ cycloalkyl.

[0108] Oligomeric HALS of formula (III) are prepared by reacting amulti-functional carbonyl compound of general structure (IV) with adiamino or a dihydroxy compound that contains the 4-aminopiperidinegroup. Preferably, the diamino or dihydroxy compound includesN,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine (BPIP) orN-(2,2,6,6-tetramethylpiperidinol) diethanolamine.

[0109] The multi-functional carbonyl compounds are prepared by anymethod available to those of ordinary skill in the art. Preferably, themulti-functional carbonyl compounds are prepared by the method of theinvention wherein a carbonyl compound is reacted with a lactam in thepresence of a Lewis acid or wherein a carbonyl compound is reacted witha lactam and an alkoxide at a low temperature, i.e., less than 20° C.The carbonyl compound, however, must have two reactive carbonyl groupsor a single carbonyl group that is activated with two leaving groups(for example, phosgene or a dialkyl carbonate). Preferably, the leavinggroup is an ester. Preferred carbonyl compound include dialkylcarbonates, dialkyl oxalates, and dialkyl esters.

[0110] The reaction can be carried out in the absence of a solvent or inthe presence of an organic solvent. When the reaction is carried out inthe absence of a solvent, either the multi-functional carbonyl compoundor the 1-substituted piperidin-4-ol or 4-aminopiperidine (for compound(II)) or the diamino or dihydroxy compound that contains the4-aminopiperidine group (for compound (III)) may be present in an excessand employed as the reaction medium. Alternatively, the multi-functionalcarbonyl compound and the 1-substituted piperidin-4-ol or4-aminopiperidine or the diamino or a dihydroxy compound that containsthe 4-aminopiperidine group can be present in stoichiometric amounts.The reaction can also be conducted in a melt.

[0111] Preferably, the reaction is carried out in an organic solvent.Any solvent compatible with the reagents may be used. Preferred solventsfor use in the method of the invention include, but are not limited to,hydrocarbon solvents such as a saturated alkanes; benzene; toluene;xylenes; halogenated hydrocarbons; ethers such as ethyl ether; cyclicethers such as tetrahydrofuran and dioxane; amides such asdimethylformamide; sulfoxides such as dimethylsulfoxide; ketones such as2-butanone or methyl isobutyl ketone; and the like; or a mixturethereof. The more preferred solvents include toluene, benzene, andxylenes, or a mixture thereof.

[0112] The concentration of the multi-functional carbonyl compound inthe organic solvent is generally present in an amount of from about0.025 M to 2.5 M, preferably from about 0.125 M to 0.2 M, and morepreferably from about 0.25 M to 1.35 M. The molar ratio of themulti-functional carbonyl compound to the 1-substituted piperidin-4-olor 4-aminopiperidine, used to prepare the oligomeric HALS of formula(II), or to the diamino or dihydroxy compound that contains the4-aminopiperidine group, used to prepare the oligomeric HALS of formula(III), is from about 5:1 to 1:5, preferably from about 2:1 to 1:2, andmore preferably from about 1.2:1 to 1:1.2.

[0113] In a preferred embodiment of the method of making the oligomericHALS of formula (II), the substituted piperidin-4-ol or4-aminopiperidine includesN-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol. In a preferredembodiment of the method of making the oligomeric HALS of formula (III),the diamino or a dihydroxy compound that contains the 4-aminopiperidinegroup 4-aminopiperidine includes BPIP or N-(2,2,6,6-tetramethylpiperidinol) diethanolamine or a mixture thereof.

[0114] Optionally, but preferably the reaction is conducted in thepresence of a catalyst. The catalyst may be a basic catalyst or an acidcatalyst. Preferably, the base catalyst is methoxide ion. Preferably theacid catalyst includes a Lewis acid. The preferred Lewis acid includes1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane.

[0115] The catalyst is typically added in an amount of less than about30 mole percent by weight based on the weight of the multi-functionalcarbonyl compound, preferably less than about 20 mole percent by weightbased on the weight of the multi-functional carbonyl compound, morepreferably less than about 10 mole percent by weight based on the weightof the multi-functional carbonyl compound, and most preferably less thanabout 5 mole percent by weight based on the weight of themulti-functional carbonyl compound.

[0116] The reaction of the multi-functional carbonyl compound and the1-substituted piperidin-4-ol or 4-aminopiperidine, used to prepare theoligomeric HALS of formula (11), or the diamino or dihydroxy compoundthat contains the 4-aminopiperidine group, used to prepare theoligomeric HALS of formula (III), is conducted for sufficient time toform a detectable amount of the oligomeric HALS of formula (II) or(III). The reaction time temperature and pressure may, readily bedetermined by one of ordinary skill in the art without undueexperimentation. Typically, the reaction time is less than about 20hours, preferably less than about 15 hours, and more preferably lessthan about 10 hours. Typically, the reaction temperature is from aboutroom temperature to about 150° C., for example, up to the boiling pointof the solvent. Preferably, the reaction is carried out at atmosphericpressure. Representative reaction conditions for forming the compound offormula (II) or (III) are provided in the examples.

[0117] After the oligomeric HALS of formula (II) or (III) are formed,they are recovered from the reaction mixture by any means available tothose of ordinary skill in the art.

[0118] In a preferred method, the oligomeric HALS of formula (II) and(III) are formed by reacting a lactam, a carbonyl compound of generalstructure

[0119] wherein m is either 0 or 1, Q is a good leaving group, such aschloride or OD, wherein D is a hydrocarbyl group, preferably methyl, andB is Q or a hydrocarbyl group and Y is CO—(CR^(e)R^(f))_(p), whereinR^(e) and R^(f) are each a hydrogen or hydrocarbyl group and p is zeroor an integer from about 1 to 20 or CO—C₆H₄—, and the substitutionpattern on the phenylene group may be an ortho, meta, or parasubstitution pattern, in addition one or more of the hydrogens of thephenylene group may be substituted by a hydrocarbyl group or otherfunctional group commonly found in organic molecules, and a1-substituted piperidin-4-ol or 4-aminopiperidine, in the case ofoligomeric HALS of formula (II), or a diamino or a dihydroxy compound,in the case of oligomeric HALS of formula (III), in a single step. Thelactam, carbonyl compound, and a 1-substituted piperidin-4-ol or4-aminopiperidine or a diamino or a dihydroxy compound that contains the4-aminopiperidine group are combined in a reaction vessel and allowed toreact for sufficient time to form a detectable amount of the compound offormula (II) or (III). The ratio of lactam to carbonyl compound is fromabout 2:1 to 1:4, preferably from about 1:1 to 1:2 and the ratio oflactam to 1-substituted piperidin-4-ol or 4-aminopiperidine or diaminoor a dihydroxy compound is from about 2:1 to 1:2, preferably about 1:1.

[0120] The single step reaction may be conducted in a solvent or in theabsence of a solvent. Preferably, the reaction is conducted in thepresence of a solvent. When a solvent is used any solvent that iscompatible with the reagents may be used. Representative solventsinclude, but are not limited to, those solvents described above for thereaction of a 1-substituted piperidin-4-ol or 4-aminopiperidine with amulti-functional carbonyl compound. When a solvent is employed, theconcentration of the lactam is typically from about 0.075 M to 10 M,preferably from about 0.375 M to 6 M, and more preferably from about0.75 M to 4 M.

[0121] Optionally, but preferably, the reaction is carried out in thepresence of a catalyst. The same catalysts may also be used as were usedin the reaction of a 1-substituted piperidin-4-ol or 4-aminopiperidinewith a multi-functional carbonyl compound. The catalyst is typicallypresent in an amount of less than about 30 mole percent, preferably lessthan about 20 mole percent, more preferably less than about 10 molepercent, and most preferably less than 5 mole percent relative to theamount of carbonyl compound.

[0122] In general the reaction time is less than about 20 hours,preferably less than about 15 hours, and more preferably less than about10 hours. Typically, the reaction temperature is from about roomtemperature to 250° C. Preferably, the reaction is carried out atatmospheric pressure. Representative reaction conditions for forming theoligomeric HALS in a single step according to the method of theinvention can readily be determined by one of ordinary skill in the art,but guidance is also provided in the examples.

[0123] When the oligomeric HALS of formula (II) or (III) is formed itmay be recovered from the reaction mixture by any means available tothose of ordinary skill in the art.

Polymeric Articles Including

[0124] HALS and Manufacture of the Same The HALS of the presentinvention, i.e., HALS of formula (I), (II), or (III) may be provided asneat compounds or may be provided in the form of a concentrate includingfrom about 15 to 98 percent by weight, and preferably from about 20 to95 percent by weight, preferably from about 25 to 90 percent by weight,and more preferably from about 40 to 70 percent of at least one of theHALS compounds of formula (I), (II), or (III) and a polymeric resin.

[0125] The HALS compounds of the present invention impart superiorweatherability and yellowing resistance to polymers. In addition, theHALS compounds of the present invention typically exhibit lowvolatility. Thus, the present invention also provides polymeric articlesstabilized by including an effective amount of the newly discovered HALScompounds to inhibit at least one of photo- or thermal degradation andmethods of making the polymeric articles. Any suitable polymercompatible with a HALS composition of the invention may be combined withone or more HALS of the invention to form a polymeric article protectedfrom UV light. The polymeric article includes at least one polymericmaterial and a sufficient amount of at least one HALS of formula (I),(II), or (III) to inhibit at least one of photo- or thermal degradation.Typically, the polymeric article is stabilized by blending from about0.01 percent to 10 percent by weight, preferably from about 0.03 percentto 1 percent by weight, and more preferably from about 0.05 percent to0.5 percent by weight of at least one HALS of formula (I), (II), or(III) with a polymeric material used to form the article. The articlemay be an extruded article, a molded article, a tape, a film, a fiber,or a coating, for example.

[0126] The method of making the polymeric articles includes blending apolymeric material with from about 0.01 percent to 10 percent by weight,preferably from about 0.03 percent to 1 percent by weight, and morepreferably from about 0.05 percent to 0.5 percent by weight at least oneHALS compounds of the present invention to form a stabilized polymericcomposition, and forming an article from the polymeric composition. Thepolymeric article may be formed by extrusion, sheet extrusion, injectionmolding, blow molding, injection blow molding, rotational orroto-molding, calendering, thermoforming, compression molding, vacuummolding, pressure molding, reaction injection molding, solvent casting,fiber spinning, and other similar techniques available to those ofordinary skill in the art. The HALS of the invention may be added to thepolymeric material by any means known in the art, and one of ordinaryskill in the art may readily envision a variety of such ways to combineone or more HALS compounds and one or more polymeric materials to formpolymeric articles according to the invention.

[0127] A variety of other conventional additives, individually or incombination, may also be added to the polymeric material. Examples ofsuch additives include, but are not limited to one or more of thefollowing classes:

[0128] a. Antioxidants

[0129] (i) Alkylated monophenols, such as2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(a-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol; nonylphenols which are liner orbranched in the side chains such as 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1-methylundec-1-yl)phenol,2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol,2,4-dimethyl-6-(1-methyltridec-1-yl)phenol, CYANOX® 1790, CYANOX® 2246,and CYANOX® 425 Antioxidants, commercially available from CYTECINDUSTRIES of West Paterson, N.J., IRGANOX® 1010 Antioxidant andIRGANOX® 1076 Antioxidant, commercially available from of CIBASPECIALTIES of Hawthorne, N.Y., and mixtures thereof;

[0130] (ii) Alkylthiomethylphenols, such as2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol, and mixtures thereof;

[0131] (iii) Hydroquinones and alkylated hydroquinones, such as2,6-di-tert-butyl-4-methoxyhenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

[0132] (iv) Tocopherols, such as a-tocopherol (vitamin E), β-tocopherol,γ-tocopherol, δ-tocopherol, and mixtures thereof;

[0133] (v) Hydroxylated thiodiphenyl ethers, such as2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide, and mixtures thereof;

[0134] (vi) Alkylidenebisphenols, such as2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxylbenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, andmixtures thereof;

[0135] (vii) O-, N- and S-benzyl compounds, such as3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, and mixturesthereof;

[0136] (viii) Hydroxybenzylate malonates, such asdioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,and mixtures thereof;

[0137] (ix) Aromatic hydroxybenzyl compounds, such as1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, and mixturesthereof;

[0138] (x) Triazine compounds, such as2,4-bis(octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, and mixturesthereof;

[0139] (xi) Benzylphosphonates, such asdimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and mixtures thereof;

[0140] (xii) Acylaminophenols, such as 4-hydroxylauranilide,4-hydroxystearanilide, and octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate, and mixtures thereof;

[0141] (xiii) Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid; β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid;β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid;3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydricalcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and mixturesthereof;

[0142] (xiv) Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid, such asN,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, andmixtures thereof;

[0143] (xv) Ascorbic acid (Vitamin C) or salt or ester thereof;

[0144] (xvi) Aminic antioxidants, such asN,N′-diisopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfonamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine such asp,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminophenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguamide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert- butyldiphenylamines,2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixtureof mono- and dialkylated tert-butyl/tert-octyl phenothiazines, a mixtureof mono- and dialkylated tert-octylphenothiazines, -allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N ,N-bis(2 ,2 ,6,6-tetramethylpiperid-4-yl)hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol,and mixtures thereof;

[0145] b. Conventional UV-absorbers and Light Stabilizers

[0146] (i) 2-(2′-Hydroxyaryl)benzotriazoles, such as2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole or2-(2H-benzotriazol-2-yl)-4-tert-octyl-phenol known as CYASORB® UV-5411Light Stabilizer, commercially available from CYTEC INDUSTRIES of WestPaterson, N.J.,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)-benzotriazole,2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole, amixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol], the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]benzotriazolewith polyethylene glycol 300, [R—CH₂CH—COO(CH₂)₃]₂— whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-yl phenyl, TINUVIN® 900Light Stabilizer, commercially available from CIBA SPECIALTIES, andmixtures thereof;

[0147] (ii) 2-Hydroxybenzophenones, for example the 4-hydroxy,4-methoxy, 4-octoxy CYASORB® UV-531 Light Stabilizer, commerciallyavailable from CYTEC INDUSTRIES), 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy compounds, and mixturesthereof;

[0148] (iii) Esters of substituted and unsubstituted benzoic acids orsalicylic acid compounds, such as 4-tert-butyl-phenyl salicylate, phenylsalicylate, octylphenyl salicylate, dibenzoyl resorcinol,bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol,2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, and2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate,and mixtures thereof;

[0149] (iv) Acrylates or alkoxyciinamates, such as ethyla-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate,methyl α-carbomethoxycinnamate, methyla-cyano-p-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate,N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, and mixtures thereof;

[0150] (v) Nickel compounds including nickel (II) complexes of aminesand thio-bis-phenols, such as nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], including the 1:1 or1:2 complex, with or without additional ligands, such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of monoalkyl esters including themethyl or ethyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes including 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands, and mixtures thereof;

[0151] (vi) Sterically hindered amines, as well as the N compoundsthereof (e.g., N-alkyl, N-hydroxy, N-alkoxy and N-acyl), such asbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione,3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione,a mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate of1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]),N-(2,2,6,6-tetramethyl piperidine-4-yl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane,oxo-piperanzinyl-triazines or so called PIP-T HALS, e.g., GOODRITE®3034, 3150 and 3159 commercially available form BF Goodrich Chemical Co.of Akron, Ohio and similar materials disclosed in U.S. Pat. No.5,071,981, photobondable HALS such as SANDUVOR® PR-31 AND PR-32commercially available from Clariant Corp. of Charlotte N.C., andsimilar materials disclosed in GB-A-2269819, the reaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decaneand epichlorohydrin. Examples of the tetramethylpiperidine derived HALSinclude CYASORB® UV-3346 Light Stabilizer, commercially available fromCYTEC INDUSTRIES, SANDUVOR® 3055 HALS, SANDUVOR® 3056 HALS, andSANDUVOR® 3058 HALS, commercially available from SANDOZ Corporation ofCharlotte, N.C., CHIMASORB® 944 Stabilizer, TINUVIN® 622 Stabilizer, andTINUVIN® 144 Stabilizer, each commercially available from CIBASPECIALTIES, and mixtures thereof. See also generally U.S. Pat. Nos.5,106,891, 4,740,542, 4,619,956, 4,426,471, 4,426,472, 4,356,307,4,344,876, 4,314,933; GB-A-2269819, EP-A-309400, EP-A-309401,EP-A-309402 and EP-A-0434608, each of which is incorporated herein byreference in their entirety;

[0152] (vii) Oxamides, oxanilides, benzoxazinones, benzoxazoles, ortriazines, such as 2,2′-(1,4-methylene)bis[4H-3,1-benzoxazin-4-one](CYASORB® UV-3638 Light Stabilizer, commercially available from CYTECINDUSTRIES), 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide,2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butyloxanilide,2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy disubstituted oxanilides and mixtures of o- and p-ethoxydisubstitutoctyloxyphenyl-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, andCYAGARD® UV-1164L Light Stabilizer, commercially available from CYTECINDUSTRIES, and mixtures thereof;

[0153] (c) Metal deactivators, such as N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide, and mixturesthereof;

[0154] (d) Phosphites and phosphonites including peroxide decomposers,such as alkyl phosphites, aryl phosphites, and aralkyl phosphites, suchas triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkylphosphites, tris(nonylphenyl) phosphite, trilauryl phosphite,trioctadecyl phosphite, distearyl pentaerythritol diphosphite ULTRANOX®618 Antioxidant, bis-(2,4-di-tert-butylphenyl)pentaerythritoldiphosphiteULTRANOX® 626 Antioxidant, commercially available from GE SpecialtyChemicals of Parkersburg, W. Va.,tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite, bis(isodecyloxy)pentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butyl)phenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite,tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2 ,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d ,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite, and mixturesthereof;

[0155] (e) Hydroxylamines, such as N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecyl-hydroxylamine,-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow fatty amines, and mixtures thereof;

[0156] (f) Nitrones, such as N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone,N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrones derived fromN,N-dialkylhydroxylamines prepared from hydrogenated tallow fattyamines, and mixtures thereof;

[0157] (g) Thiosynergists, such as dilauryl thiodipropionate anddistearyl thiodipropionate, and mixtures thereof;

[0158] (h) Peroxide scavengers such as esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(p-dodecylmercapto)propionate, and mixtures thereof;

[0159] (i) Polyamide stabilizers, such as copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese, and mixtures thereof;

[0160] (j) Basic co-stabilizers, such as melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea compounds, hydrazine compounds,amines, polyamides, polyurethanes, alkali metal salts and alkaline earthmetal salts of higher fatty acids, for example calcium stearate, zincstearate, magnesium behenate, magnesium stearate, sodium ricinoleate andpotassium palmitate, antimony pyrocatecholate, tin pyrocatecholate, andmixtures thereof;

[0161] (k) Nucleating agents including inorganic substances, such astalc and metal oxides (e.g., titanium oxide or magnesium oxide), andphosphates, carbonates and sulfates of, preferably, alkaline earthmetals; organic compounds, such as mono- or polycarboxylic acids andsalts thereof, for example 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate and sodium benzoate; polymericcompounds such as ionic copolymers (“ionomers”), and mixtures thereof;

[0162] (l) Fillers and reinforcing agents, such as calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite, wood flour andflours or fibers from other natural products, and synthetic fibers, andmixtures thereof;

[0163] (m) Benzofuranones and indolinones, such as those disclosed inU.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, and5,252,643, and DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839and EP-A-0591102;3-[4-(2-acetoxy-ethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)-phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,and mixtures thereof;

[0164] (n) Sulfur containing antioxidants, such as organic sulfides anddisulfides and include distearyl thiodipropionate CYANOX® STDPAntioxidant, commercially available from CYTEC INDUSTRIES,pentaerythritol tetrakis(beta-laurylthiopropionate) SEENOX® 412 SAntioxidant, commercially available from Witco Chemical Corporation ofBrooklyn, N.Y., and mixtures thereof. A person skilled in the art iswell aware, for example, that any one or more of these additives may becombined, such as in CYANOX® 2777 Antioxidant, commercially availablefrom CYTEC INDUSTRIES, which combines a phenolic antioxidant and aphosphite antioxidant. The composition may contain quenchers such asCYASORB® UV-1084 Light Stabilizer, CYASORB® UV-531 Light Stabilizer,each commercially available from CYTEC INDUSTRIES.

[0165] (o) Other additives, such as acid scavengers, antistatic agents,blowing agents, catalysts, clarifying agents, emulsifiers, fillers,flameproofing agents, fluorescent whitening agents, infrared absorbers,levelling assistants, lubricants, metal deactivators, mold releaseagents, nucleating agents, optical brighteners, pigments, plasticizers,rheological additives, and mixtures thereof.

[0166] The total amount of additives may be present in an amount up toabout 10 percent, preferably from about 0.1 percent to about 5 percentby weight, and more preferably from about 0.2 percent to 3 percent byweight, based on the weight of the polymer.

[0167] The light-stabilized polymeric article may be formed from apolymeric material by incorporating the presently claimed compounds intopolymeric materials, either chemically or physically. Non-limitingexamples of polymeric materials that may be so stabilized arepolyolefins; polyesters; polyethers; polyketones; polyamides; naturaland synthetic rubbers; polyurethanes; polystyrenes; high-impactpolystyrenes; polyacrylates; polymethacrylates; polyacetals;polyacrylonitriles; polybutadienes; polystyrenes; ABS; SAN (styreneacrylonitrile); ASA (acrylate styrene acrylonitrile); cellulosic acetatebutyrate; cellulosic polymers; polyimides; polyamideimides;polyetherimides; polyphenylsulfides; PPO; polysulfones;polyethersulfones; polyvinylchlorides; polycarbonates; polyketones;aliphatic polyketones; thermoplastic TPO's; aminoresin crosslinkedpolyacrylates and polyesters; polyisocyanate crosslinked polyesters andpolyacrylates; phenol/formaldehyde, urea/formaldehyde, andmelamine/formaldehyde resins; drying and non-drying alkyd resins; alkydresins; polyester resins; acrylate resins cross-linked with melamineresins, urea resins, isocyanates, isocyanurates, carbamates, and epoxyresins; cross-linked epoxy resins derived from aliphatic,cycloaliphatic, heterocyclic and aromatic glycidyl compounds which arecross-linked with anhydrides or amines; polysiloxanes; Michael additionpolymers of amines or blocked amines with activated unsaturated andmethylene compounds, ketimines with activated unsaturated and methylenecompounds, polyketimines in combination with unsaturated acrylicpolyacetoacetate resins, and polyketimines in combination withunsaturated acrylic resins; radiation curable compositions;epoxymelamine resins; organic dyes; cosmetic products; cellulose-basedpaper formulations; photographic film paper; ink; and blends thereof.

[0168] The degradable polymer may be any polymer requiringstabilization, and includes homopolymers and copolymers of variousmonomers. It may be an addition polymer, a condensation polymer, a graftpolymer, a thermosetting polymer, a photopolymer, a polymer blend or athermoplastic polymer. It may be in the form of a fiber, a polymer filmsuch as polypropylene films, a thin film such a solvent based coating, awater-based coating, a stoving lacquer, a powder coating, a gel coat,and the like, or it may be in the form of a molded article. Examples ofdegradable polymers which can be stabilized include, but are not limitedto:

[0169] 1. Homo- and copolymers of monoolefins and diolefins including,but not limited to, ethylene, propylene, isobutylene, butene,methylpentene, hexene, heptene, octene, isoprene, butadiene, hexadiene,dicyclopentadiene, ethylidene, and cycloolefins such as cyclopentene andnorbornene; for example, polyethylenes (which optionally can becross-linked) such as high density polyethylene (HDPE), high density andhigh molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), branched low density polyethylene (BLDPE) orpolypropylene (PP) or polymers of ethylene propylene diene monomer(EPDM); and blends thereof.

[0170] 2. Copolymers of one or more monoolefins and/or diolefins withcarbon monoxide and/or with other vinyl monomers, including acrylic andmethacrylic acid, acrylates and methacrylates, acrylamides,acrylonitriles, styrenes, vinyl acetate (such as ethylene/vinyl acetatecopolymers (EVA)), vinyl halides, vinylidene halides, maleic anhydride,and allyl monomers such as allyl alcohol, allyl amine, allyl glycidylether and compounds thereof; and blends thereof.

[0171] 3. Hydrocarbon resins (such as C₅-C₉) including hydrogenatedmodifications thereof, and mixtures of polyalkylenes and starch; andblends thereof.

[0172] 4. Homo- and copolymers of styrenes such as styrene,p-methylstyrene and α-methylstyrene such as polystyrene,polyalphamethylstyrene, high impact polystyrene (HIPS); and blendsthereof.

[0173] 5. Copolymers of one or more styrenes with other vinyl monomerssuch as olefins and diolefins (e.g., ethylene, isoprene and/orbutadiene), acrylic and methacrylic acid, acrylates and methacrylates,acrylamides, acrylonitriles, vinyl acetate (such as ethylene/vinylacetate copolymers), vinyl halides, vinylidene halides, maleic anhydrideand allyl compounds such as allyl alcohol, allyl amine, allyl glycidylether; and blends thereof.

[0174] 6. Graft copolymers of styrenes on polybutadienes,polybutadiene/styrene copolymers and polybutadiene/acrylonitrilecopolymers; styrene (or α-methylstyrene) and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; acrylonitrile/styrene/acrylonitrile polymers (ASA)styrene and acrylonitrile on ethylene/propylene/diene copolymers;styrene and acrylonitrile on polyalkyl acrylates or methacrylates; andstyrene and acrylonitrile on acrylate/butadiene (ABS) copolymers; andblends thereof.

[0175] 7. Halogen-containing polymers such as poly vinyl chloride (PVC),chlorinated polyethylene (CPE), or polychloroprene; chlorinated rubbers;chlorinated and brominated isobutylene/isoprene copolymers; chlorinatedor sulfochlorinated polyethylene; copolymers of ethylene and chlorinatedethylene; epichlorohydrin polymers and copolymers; and polymers andcopolymers of halogen-containing vinyl compounds such as vinyl chloride,vinylidene chloride, vinyl fluoride and/or vinylidene fluoride, othervinyl monomers or other polyvinyl halides; and blends thereof.

[0176] 8. Homo- and copolymers derived from α,β-unsaturated acids andcompounds thereof such as acrylic acid, methacrylic acid, acrylates,methacrylates, acrylamides and acrylonitriles; and blends thereof.

[0177] 9. Copolymers of the monomers mentioned in (5) above with otherunsaturated monomers such as olefins and diolefins (e.g., butadiene),styrenes, vinyl halides, maleic anhydride and allyl monomer such asallyl alcohol, allyl amine, allyl glycidyl ether; and blends thereof.

[0178] 10. Homo- and copolymers derived from unsaturated alcohols andamines or the acyl compounds or acetals thereof, such as vinyl alcohol(including polyvinyl alcohol cross-linked polyvinyl alcohol), vinylacetate, vinyl stearate, vinyl benzoate, vinyl maleate, vinyl butyral,allyl alcohol, allyl amine, allyl glycidyl ether, allyl phthalate andallyl melamine; as well as copolymers of such monomers with otherethylenic unsaturated monomers mentioned above; and blends thereof.

[0179] 11. Homo- and copolymers of cyclic ethers such as alkyleneglycols and alkylene oxides, as well as copolymers with bisglycidylethers; and blends thereof.

[0180] 12. Polyacetals such as polyoxymethylene (POM) and thosepolyoxymethylenes which contain ethylene oxide as a comonomer; andpolyoxyinethylenes modified with thermoplastic polyurethanes, acrylatesand/or MBS; and blends thereof.

[0181] 13. Polyphenylene oxides (PPO) and sulfides; and blends thereof.

[0182] 14. Polyurethanes (PUR) derived from hydroxy-functionalcomponents such as polyhydric alcohols, polyethers, polyesters,polyacrylics and/or polybutadienes on the one hand, and aliphatic and/oraromatic isocyanates on the other, as well as precursors thereofincluding isocyanate cross-linked polymers; and blends thereof.

[0183] 15. Polyamides (PA) and copolyamides derived from diamines,dicarboxylic acids and/or aminocarboxylic acids or the correspondinglactams, such as NYLON® plastics, e.g., polyamide 4, polyamide 6,polyamide 6/6, polyamide 6/10, polyamide 6/9, polyamide 6/12, polyamide4/6, polyamide 12/12, polyamide 11 and polyamide 12; aromatic polyamidesstarting from m-xylene diamine and adipic acid; polyamides prepared fromhexamethylene diamine and isophthalic and/or terephthalic acid and withor without an elastomer as a modifier, for example,poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; block copolymers of the aforementioned polyamides withpolyolefins, olefin copolymer, ionomers, chemically bonded or graftedelastomers, or polyethers such as polyepoxides, polyethylene glycol,polypropylene glycol or polytetramethylene glycol; and polyamidescondensed during processing (RIM polyamide systems); and blends thereof.

[0184] 16. Polyureas, polyimides, polyamide-imides, polyetherimides,polyesterimides, polyhydantoins and polybenzimidazoles; and blendsthereof.

[0185] 17. Polyesters derived from dicarboxylic acids, diols and/orhydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate (PET), polybutylene terephthalate (PBT),polyethylene terephthalate, glycol modified (PETG), polyethyleneterephthalate modified with 1,4-cyclohexanedimethanol(PCTG),poly-1,4-dimethylcyclohexane terepthalate andpolyhydroxybenzoates, as well as block copolyether esters derived fromhydroxyl-terminated ethers; and also polyesters modified withpolycarbonate or MBS; PEN, PTT; and blends thereof.

[0186] 18. Polycarbonates (PC) and polyester carbonates such as resinsare polycarbonates based on dihydric phenols such as2,2-bis-(4-hydroxyphenyl)propane (bisphenol A); 2,4-bis(4-hydroxyphenyl)-2-methylbutane; 1,1-bis-(4-hydroxyphenyl)-cyclohexane;2,2-bis-(3-chloro-4-hydroxyphenyl)propane; 4,4′-sulfonyldiphenol; and1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; and blendsthereof. Also preferred are polycarbonate copolymers incorporating twoor more phenols, branched polycarbonates wherein a polyfunctionalaromatic compound is reacted with a dihydric phenol(s) and carbonateprecursor, and polymer blends of which polycarbonate comprises asignificant portion of the blend (i.e., more than 20%, preferably morethan 50%). Preferred resins for both layers are polycarbonates based onbisphenol A.

[0187] U.S. Pat. No. 5,288,788 also describes polycarbonates andpolyester carbonates, especially aromatic polycarbonates, for examplethose based on 2,2-bis(4-hydroxyphenyl)propane or1,1-bis(4-hydroxyphenyl)cyclohexane. Mixtures (polyblends) of suchpolymers with one another or with other polymers, for example withpolyolefins, polyacrylates, polydienes or other elastomers in the formof impact strength modifiers can also be stabilized with the HALScompounds of the invention.

[0188] Among those compounds, preference is given to the polycarbonates,polyesters, polyamides, polyacetals, polyphenylene oxides andpolyphenylene sulfides, but especially to the polycarbonates. Thosecompounds are to be understood as being especially those polymers theconstitutional repeating unit of which corresponds to the formula:

[0189] wherein A is a divalent phenolic radical. Suitable examples of Aare given in U.S. Pat. No. 4,960,863 and DE-A-3922,496 whose contentsare incorporated herein by reference thereto “A” can be derived, forexample, from hydroquinone, resorcinol, dihydroxybiphenylene orbisphenols in the broadest sense of the term, such asbis(hydroxyphenyl)alkanes, cycloalkanes, sulfides, ethers, ketones,sulfones, sulfoxides, α,α′-bis(hydroxyphenyl)-diisopropylbenzenes, forexample the compounds 2,2-bis(4-hydroxyphenyl)propane,2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-propane,2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,1,1-bis(4-hydroxypehnyl)cyclohexane, or from the compounds of theformula:

[0190] 19. Polysulfones, polyether sulfones and polyether ketones.

[0191] 20. Cross-linked polymers derived from aldehydes condensationresins such as phenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins; and blends thereof.

[0192] 21. Drying and non-drying alkyd resins; and blends thereof.

[0193] 22. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof; and blends thereof.

[0194] 23. Cross-linkable acrylic resins derived from substitutedacrylates such as epoxy acrylates, hydroxy acrylates, isocyanatoacrylates, urethane acrylates or polyester acrylates; and blendsthereof.

[0195] 24. Alkyd resins, polyester resins and acrylate resinscross-linked with melamine resins, urea resins, isocyanates,isocyanurates, carbamates or epoxy resins; and blends thereof.

[0196] 25. Cross-linked epoxy resins derived from aliphatic,cycloaliphatic, heterocyclic and/or aromatic glycidyl compounds such asbisphenol A and bisphenol F, which are cross-linked with customaryhardeners such as anhydrides or amines; and blends thereof.

[0197] 26. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous compounds thereof, including celluloseacetates, cellulose propionates and cellulose butyrates, nitrocellulose,or the cellulose ethers such as methyl cellulose, as well as rosins andtheir compounds; and blends thereof.

[0198] 27. Polysiloxanes; and blends thereof.

[0199] 28. Michael addition polymers of amines or blocked amines (e.g.,ketimines) with activated unsaturated and/or methylene compounds such asacrylates and methacrylates, maleates and acetoacetates; and blendsthereof.

[0200] 29. Mixtures or blends of any of the above, such as PP/EPDM,polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS,PC/ASA,

[0201] PC/PBT, PVC/CPE, PVC/acrylate, POM/thermoplastic PUR,PC/thermoplastic polyurethane, POM/acrylate, POM/MBS, PPO/HIPS,PPO/PA6.6 and copolymers, PA/HDPE, PP/HDPE, PP/LDPE, LDPE/HDPE,LDPE/EVA, LDPE/EAA, PA/PP, PA/PPO, PBT/PC/ABS, PBT/PET/PC and the like.

[0202] 30. Naturally occurring and synthetic organic materials which maybe mixtures of compounds, including mineral oils, animal and vegetablefats, oils and waxes, or oils, fats or waxes based on synthetic esters(e.g., phthalates, adipates, phosphates or trimellitates) and alsomixtures of synthetic esters with mineral oils in any ratio.

[0203] 31. Aqueous emulsions of natural or synthetic rubber such asnatural latex or latexes of carboxylated styrene/butadiene copolymers;and blends thereof.

[0204] 32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins includingurethane acrylates, polyether acrylates, vinyl or acryl copolymers withpendant unsaturated groups and acrylated melamines; and blends thereof.

[0205] 33. Radiation curable compositions containing ethylenicallyunsaturated monomers or oligomers and a polyunsaturated aliphaticoligomer; and blends thereof.

[0206] 34. Epoxymelamine resins such as light-stable epoxy resinscross-linked by an epoxy functional coetherified high solids melamineresin. The aminoresin-cross-linked polymer may be anaminoresin-cross-linked thermoset acrylic or an aminoresin-cross-linkedthermoset polyester. The suitable aminoresins include alkylated andunalkylated melamine-formaldehyde resins, guanamine-formaldehyde resins,urea-formaldehyde resins, glycouril formaldehyde resins, and the like;and blends thereof.

[0207] 35. Organic dyes such as azo dyes (diazo, triazo, and polyazo),anthraquinones, benzodifuranones, polycyclic aromatic carbonyl dyes,indigoid dyes, polymethines, styryl dyes, di- and triaryl carboniumdyes, phthalocyanines, quinophthalones, sulfur dyes, nitro and nitrosodyes, stilbene dyes, formazan dyes, quinacridones, carbazoles, andperylene tetracarboxylic diimides; and blends thereof.

[0208] 36. Cosmetic products, such as skin lotions, collagen creams,sunscreen, facial make-up, etc., comprising synthetic materials such asantioxidants, preservatives, lipids, solvents surfactants, colorants,antiperspirants, skin conditioners, moisturizers etc.; as well asnatural products such as collagen, proteins, mink oil, olive oil,coconut oil, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum,aloe, etc; and blends thereof.

[0209] 37. Cellulose-based paper formulations for use, e.g., innewsprint, cardboard, posters, packaging, labels, stationery, book andmagazine paper, bond typing paper, multi-purpose and office paper,computer paper, xerographic paper, laser and inkjet printer paper,offset paper, currency paper, etc., and combinations thereof.

[0210] 38. Photographic film paper.

[0211] 39. Ink.

[0212] The term “copolymer,” as used herein, is a polymer of two or moredifferent monomers. Preferably, the light-stabilized polymeric materialis formed from a polyolefin homopolymer or copolymer, and morepreferably a homopolymer or copolymer of polyethylene or polypropylene.

[0213] The novel HALS of the present invention can also be employed inmultilayer systems. In such systems, a polymer composition having fromabout 0.1 to 20 percent by weight and preferably having a relativelyhigh content of the novel HALS of the invention, for example, from about5 to 15 percent by weight, is applied in a thin film (typically betweenabout 5 to 500 μm and preferably from about 10 to 100 μm thick) to ashaped article made from a polymer containing little or no ultravioletstabilizers. Such composition may be applied at the same time as theshaping of the base structure, for example by coextrusion.Alternatively, application can also be made to the ready-formed basestructure, for example by lamination with a film or by coating with asolution. The outer layer or layers of the finished article have thefunction of a UV filter, which protects the interior of the article fromUV light. The outer layer preferably contains about 0.1 to 20 percent,preferably about 1 to 15 percent and more preferably about 2 to 10percent by weight of the outer layer composition, of at least one of theHALS of the present invention.

[0214] British Patent Appn. No. 2,290,745 describes a number of methodsthat have been developed to concentrate UV absorbers near or at thesurface of polymeric materials. These include surface impregnation (seeU.S. Pat. Nos. 3,309,220, 3,043,709, 4,481,664 and 4,937,026) andcoating a plastic article with solutions containing thermoplastic resinsand UV absorbers (see U.S. Pat. Nos. 4,668,588 and 4,353,965). Bothtechniques, however, suffer from drawbacks such as requiring additionalprocessing steps (i.e., applying, drying or curing), and encounterdifficulties associated with the handling of large processed articles.An additional drawback, particularly relevant to polycarbonate sheetproduction, is the detrimental effect such post addition treatment wouldhave on the surface of the polymeric substrate.

[0215] As described in the U.S. Pat. No. 5,445,872, application ofsurface layers via coextrusion takes place in a known manner with knowncoextrusion equipment as taught in U.S. Pat. Nos. 3,487,505 and 3,557,265, which is a preferred way to incorporate HALS compounds onto thesurface of a polymeric article according to the present invention.Coextrusion is a well recognized method of producing laminatedthermoplastic materials by simultaneously extruding various numbers oflayers which form a single composite material. U.S. Pat. No. 4,540,623describes coextruded materials of at least forty layers. Other methodsknown to those of ordinary skill in the art produce as few as two orthree different layers.

[0216] In one embodiment, the invention relates to thermoplasticarticles coated with a thermoplastic layer about 0.1 to 10 mil (0.00254mm to 0.254 mm) thick, preferable about 0.1 to 5 mil (0.00254 mm to0.127 mm) thick, in which the layer contains between about 0.1% to 20%by weight of one or more of the HALS of the invention. Preferredconcentrations are from about 2% to 15% by weight; most preferred areconcentrations from about 5% to 10% by weight.

[0217] The HALS of the instant invention may be incorporated into thethermoplastics of the surface layer by standard methods, such as drymixing the additives with a granular resin prior to extruding. The HALSlayer may be applied to one or more sides of a thermoplastic articleaccording to the present invention.

[0218] Laminated thermoplastic articles corresponding to the presentinvention which contain additional layers such as a water resistantlayer, as found in U.S. Pat. No. 4,992,322, are also within the scope ofthe present invention.

[0219] The core layer and the coating layer may be of the samethermoplastic resin or different. Examples of thermoplastic resinsinclude thermoplastic polyesters, polyester carbonates, polyphenyleneoxide, polyvinyl chloride, polypropylene, polypropylene, polyethylene,polyacrylates, polymethacrylates and copolymers and blends such asstyrene and acrylonitrile on polybutadiene and styrene with maleicanhydride; and blends thereof.

[0220] The polymers stabilized in this way are notable for highweathering resistance, especially for high resistance to UV light. Thisenables them to substantially retain their mechanical properties andtheir color and gloss for a long time even when used in harshenvironments.

Coating Stabilizers Including HALS Compounds and Preparation of the Same

[0221] In another embodiment of the present invention, novel mixturescomprising at least one HALS of the invention can be used as stabilizersfor coatings, for example for paints. Of particular interest arecoatings and paints for the automobile industry. “Coating” means a freeflowing composition that can be applied to the surface of an article ina thin film that then hardens to form a substantially solid surface onthe article. Typically, the coating provides an interface between thearticle and the environment.

[0222] Such novel coating compositions comprise from about 0.01 to 20percent, preferably from about 0.01 to 10 percent and more preferablyfrom about 0.02 to 5 percent by weight of one or more of the HALS of thepresent invention.

[0223] The coating may be applied to the surface of the article in oneor more than one layer to provide a multilayered system. In multilayersystems, the concentration of the novel HALS compounds in the outerlayer can be relatively high, for example from about 0.01 to 20 percent,preferably from about 0.01 to 10 percent, and more preferably from about0.02 to 5 percent by weight.

[0224] The use of the novel stabilizer in coatings is accompanied by theadditional advantage that it inhibits or prevents delamination, i.e.,the flaking-off of the coating from the substrate. This advantage isparticularly important in the case of metallic substrates, includingmultilayer systems on metallic substrates, which have such flakingtendencies.

[0225] The coatings typically include a binder that suspends pigmentsand other additives in the coating and allows attachment of the coatingto the substrate.

[0226] The binder can in principle be any binder which is customary inindustry, for example those described in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim,1991, which is incorporated herein by reference. In general, it is afilm-forming binder based on a thermoplastic or thermosetting resin,predominantly on a thermosetting resin. Examples thereof are alkyd,acrylic, polyester, phenolic, melamine, epoxy, and polyurethane resins,and mixtures thereof.

[0227] Such binders can be a cold-curable or hot-curable binder.Further, in some systems it may be advantageous to add a curing catalystto such systems. Suitable catalysts which accelerate curing of thebinder are described, for example, in Ullmann's Encyclopedia ofIndustrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft,Weinheim, 1991, which is incorporated herein by reference.

[0228] Preferred binders include those which comprise a functionalacrylate resin and a crosslinking agent.

[0229] A wide variety of binders may be employed in such coatingsystems. Examples of suitable coating compositions containing specificbinders, include but are not limited to:

[0230] 1. paints based on cold- or hot-cross-linkable alkyd, acrylate,polyester, epoxy or melamine resins, or mixtures of such resins, ifdesired with addition of a curing catalyst;

[0231] 2. two-component polyurethane paints based on hydroxyl-containingacrylate, polyester or polyether resins and aliphatic or aromaticisocyanates, isocyanurates or polyisocyanates; or mixtures thereof;

[0232] 3. one-component polyurethane paints based on blockedisocyanates, isocyanurates or polyisocyanates which are deblocked duringbaking; or mixtures thereof;

[0233] 4. two-component paints based on (poly)ketimines and aliphatic oraromatic isocyanates, isocyanurates or polyisocyanates; or mixturesthereof;

[0234] 5. two-component paints based on (poly)ketimines and anunsaturated acrylate resin or a polyacetoacetate resin or amethacrylamidoglycolate methyl ester; or mixtures thereof;

[0235] 6. two-component paints based on carboxyl- or amino-containingpolyacrylates and polyepoxides; or mixtures thereof;

[0236] 7. two-component paints based on acrylate resins containinganhydride groups and on a polyhydroxy or polyamino component; ormixtures thereof;

[0237] 8. two-component paints based on (poly)oxazolines and acrylateresins containing anhydride groups, or unsaturated acrylate resins, oraliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; ormixtures thereof;

[0238] 9. two-component paints based on unsaturated polyacrylates andpolymalonates; or mixtures thereof;

[0239] 10. thermoplastic polyacrylate paints based on thermoplasticacrylate resins or externally crosslinking acrylate resins incombination with etherified melamine resins; or mixtures thereof;

[0240] 11. paint systems based on siloxane-modified or fluorine-modifiedacrylate resins or mixtures thereof;.

[0241] In addition to the binder and novel HALS of the presentinvention, the coating composition according to the invention mayfurther comprise one or more additional additives, such as anantioxidant or additional ultraviolet light absorber or stabilizer.Additional additives include, but are not limited to, those specificallylisted above. The additional additive is employed in coatingcompositions in an amount of from about 0.01 to 5 percent, preferablyfrom about 0.02 to 2 percent by weight.

[0242] In addition, well known to those of ordinary skill in the art tobe suitable for coating compositions the coating composition can alsocomprise further components including, but not limited to, solvents,pigments, dyes, plasticizers, stabilizers, thixotropic agents, dryingcatalysts and/or leveling agents, or combinations thereof. Examples ofpossible components are those described in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim1991, which is incorporated herein by reference.

[0243] Exemplary drying catalysts or curing catalysts are, for example,organometallic compounds, amines, amino-containing resins and/orphosphines. Examples of organometallic compounds are metal carboxylates,especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metalchelates, especially those of the metal Al, Ti or Zr, or organometalliccompounds such as organotin compounds, for example, and mixturesthereof.

[0244] Examples of metal carboxylates are the stearates of Pb, Mn or Zn,the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or thecorresponding linoleates, resinates or tallates, and mixtures thereof.

[0245] Examples of metal chelates are the aluminum, titanium, orzirconium chelates of acetylacetone, ethyl acetylacetate,salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone, or ethyltrifluoroacetylacetate, and the alkoxides of these metals, and mixturesthereof.

[0246] Examples of organotin compounds are dibutyltin oxide, dibutyltindilaurate or dibutyltin dioctoate, and mixtures thereof.

[0247] Examples of amines are, in particular, tertiary amines, forexample tributylamine, triethanolamine, N-methyldiethanolamine,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine ordiazabicyclooctane (triethylenediamine) and salts thereof, and mixturesthereof. Further examples are quaternary ammonium salts, for exampletrimethylbenzylammonium chloride. Amino-containing resins aresimultaneously a binder and a curing catalyst. Examples thereof areamino-containing acrylate copolymers.

[0248] The curing catalyst used can also be a phosphine, for exampletriphenylphosphine.

[0249] The novel coating compositions can also be radiation-curablecoating compositions. In this case, the binder includes monomeric oroligomeric compounds containing ethylenically unsaturated bonds, whichafter application are cured by actinic radiation, i.e., converted into acrosslinked, high molecular weight form. Where the system is UV-curable,it generally contains a photoinitiator as well. Corresponding systemsare described in the above-mentioned publication Ullmann's Encyclopediaof Industrial Chemistry, 5th Edition, Vol. A18, pages 451-453, which isincorporated herein by reference. In radiation-curable coatingcompositions, the novel stabilizers can also be employed with or withoutadditional UV light stabilizers, including sterically hindered amines.

[0250] The coating compositions according to the invention can beapplied to any desired substrates, for example to metal, wood, plastic,or ceramic materials. They are preferably used as topcoats in thefinishing of automobiles. If the topcoat comprises two layers, of whichthe lower layer is pigmented and the upper layer is not pigmented, thenovel coating composition can be used for either the upper or the lowerlayer or for both layers, but preferably for the upper layer.

[0251] The novel coating compositions can be applied to the substratesby any conventional methods available to those or ordinary skill in theart, for example by brushing, spraying, pouring, dipping, orelectrophoresis; see also Ullmann's Encyclopedia of IndustrialChemistry, 5th Edition, Vol. A18, pp. 491-500, which is incorporatedherein by reference.

[0252] Depending on the binder system, the coatings can be cured at roomtemperature or may require heating. The coatings are preferably cured ata temperature of from about 5⁰° C. to 150° C., and in the case of powdercoatings, even at higher temperatures.

[0253] The coatings obtained in accordance with the invention generallyhave excellent resistance to the damaging effects of light, oxygen, andheat. In particular, the presently claimed coatings provide good lightstability and weathering resistance.

[0254] The invention therefore encompasses coatings, in particular apaint, which has been stabilized against the damaging effects of light,oxygen, and/or heat by a content of at least one of the HALS of thepresent invention incorporated into or onto an article. The paint may bea pigmented mono-coat which includes a film-forming binder and anorganic pigment or dye, an inorganic pigment, a metallic pigment, or amixture thereof. The paint may also be a composition which comprises aprimer in adhesion to a metal or plastic substrate; a pigmented basecoat that is in adhesion to the primer, and which comprises afilm-forming binder and an organic pigment or dye, an inorganic pigment,a metallic pigment, or a mixture thereof; and a clear top coat that isin adhesion to the base coat, and which comprises a film-forming binderand optionally a transparent pigment. The paint is preferably a topcoatfor automobiles.

[0255] The invention furthermore relates to a process for stabilizing acoating based on organic polymers against damage by light, oxygen,and/or heat, which comprises mixing with the coating composition amixture comprising one or more HALS of the present invention, as well asthe use of mixtures comprising the one or more HALS of the presentinvention in coating compositions as stabilizers against damage bylight, oxygen, and/or heat.

[0256] The coating compositions can comprise an organic solvent orsolvent mixture in which the binder is soluble. The coating compositioncan otherwise be an aqueous solution or dispersion. The carrier can alsobe a mixture of organic solvent and water. The coating composition maybe a high-solids paint or can be solvent-free (e.g., a powder coatingmaterial).

[0257] The pigments can be inorganic, organic or metallic pigments. Thenovel coating compositions preferably contain no pigments and preferablyare used in clearcoat compositions.

[0258] Likewise preferred is the use of the coating composition as atopcoat for applications in the automobile industry, especially as apigmented or unpigmented topcoat of the paint finish. Its use forunderlying coats, however, is also possible.

EXAMPLES

[0259] The following examples are merely illustrative of preferredembodiments of the present invention and are not to be construed aslimiting the invention, the scope of which is defined by the appendedclaims.

Examples 1-9 Preparation of HALS Compounds based on Multi-FunctionalCarbonyl Compounds

[0260] Eight HALS compounds of the general structure depicted below weresynthesized according to the invention.

[0261] Compound I (n=5, R=hydrogen)

[0262] Compound II (n=5, R=methyl)

[0263] Compound III (n=11, R=hydrogen)

[0264] Compound IV (n=11, R=methyl)

[0265] wherein i, j, k, and l are integers and the sum of i, j, k, and lis greater than 2.

[0266] Compound VII (Mn=approximately 2,000)

[0267] Compound VIII (Mn=approximately 8,800)

[0268] Compounds I and II were prepared from methyl6-(methoxycarbonylamino) hexanoate (Compound A), compounds III and IVwere prepared from butyl 6-butoxycarbonylaminoundecanoate (Compound B),compound V was prepared from methyl6-[(methoxyoxoacetyl)amino]-hexanoate (Compound C) and compound VI wasprepared from methyl 6-(octanoylamino)bexanoate (Compound D). CompoundsVII and VIII were prepared from compound A andN-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol.

[0269] Compound A (n=5, R=methyl)

[0270] Compound B (n=11, R=butyl)

[0271] N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol was preparedby the hydrolysis of TINUVIN 622 with aqueous sodiumhydroxide/tetrahydrofuran, removal of the tetrahydrofuran under reducedpressure, extraction of the aqueous layer with chloroform, drying andfiltering the chloroform layer, and removal of the chloroform underreduced pressure. The recoveredN-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol had a melting pointof 179-183° C. (literature melting point 182° C., DE 2,352,658). Thesynthesis of Compounds A, B, C and D are described below.

[0272] Synthesis of Compound A:

[0273] To a 300 mL 3-necked round bottom flask equipped with amechanical stirrer, a ground glass stopper and a condenser fitted withan argon inlet and outlet to a bubbler was charged 10 g (88 mmol) ofcaprolactam, 10.5 g (117 mmol) of dimethylcarbonate, 5.23 g (96.8 mmol)of sodium methoxide, and 100 mL of methanol. The mixture was heated atreflux for 24 hours, then cooled to room temperature. 7.3 g (121 mmol)of glacial acetic acid was added and the methanol removed by rotaryevaporation. The residue was dissolved in 100 mL of methylene chlorideand the organic layer extracted with water to remove unreactedcaprolactam. Solvent removal by rotary evaporation, followed by furthersolvent removal in vacuo (<1 mm) at 95° C. gave 5.23 g (29%) of compoundA as a nearly colorless oil. The structure of compound A was establishedby NMR. ¹H NMR (CDCI₃): δ 4.63 (br s, 1H, NH); 3.68 (s, 3H, CH₃—OCO);3.66 (s, 3H, CH₃—OCO); 3.17 (br dt, 2H, —CH₂—NH—); 2.31 (t, 2H,—CH₂COO); 1.65-1.21 (in, 6H, CH₂(CH ₂)₃CH₂).

[0274] Synthesis of Compound B:

[0275] To a three-necked, 250 mL reaction flask equipped with a magneticstirrer, a reflux condenser, and a thermometer adapter, was charged13.96 g (0.070 mol) of laurolactam, 13.4 g (0.076 mol) of dibutylcarbonate, 4.16 g (0.077 mol) of sodium methoxide, and 130 g of butanol.The mixture was heated for 64 hours at 110° C. After cooling to roomtemperature, 4.9 g (0.10 mol) of glacial acetic acid in 30 g of butanolwas added and the mixture stirred for 5 min. The resulting mixture wasdiluted with 500 mL of methylene chloride, washed with water, and dried(MgSO₄). Filtration and rotary evaporation gave 19.6 g of a greasysolid. Flash chromatography on 200-400 mesh, 60 Å silica gel (0.5%methanol/methylene chloride) gave 7.2 g (25%) of the title compound as awhite semi-solid. The structure of compound B was established by NMR. ¹HNMR (CDCI₃): δ 4.61 (br s, 1H, NH); 4.05 (q, 4H, —CH₂CH₂—OCO); 3.16 (brdt, 2H, —CH ₂—NH—); 2.28 (t, 2H, —CH₂COO); 1.65-1.21 (m, 26H, CH₂(CH₂)₉CH₂, (CH ₂)₂CH ₃), 0.93 (t, 6H, CH₃).

[0276] Synthesis of Compound C:

[0277] To a 100-mL round bottom flask equipped with a stir bar wascharged 8.45 g (75 mmol) of caprolactam, 8.85 g (75 mmol) of dimethyloxalate, and 0.16 g (3 mmol) of sodium methoxide. The mixture wasimmersed in a 50° C. oil bath and heated for 30 min, then cooled over anhour to 35° C. After stirring at this temperature for several hours, themixture was cooled and allowed to stand overnight at room temperature.The mixture was diluted with 125 mL of methylene chloride and washedwith water, then washed with saturated sodium chloride solution. Dryingover molecular sieves, filtration, and removal of solvent under reducedpressure gave 12.5 g (72% yield) of a light yellow liquid whichcrystallized to a low melting solid on standing. The structure of thematerial was confirmed by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 7.18 (br s,1H, NH); 3.90 (s, 3H, CH₃—OCOCO); 3.67 (s, 3H, CH₃—OCCH₂); 3.35 (app q,2H, —CH ₂—NH—); 2.32 (t, 12H, —CH₂COO); 1.70-1.30 (m, 6H, CH₂(CH₂)₃CH₂).

[0278] Synthesis of Compound D:

[0279] To a 100-mL round bottom flask equipped with a stir bar wascharged 16.9 g (150 mmol) of caprolactam, 23.7 g (150 mmol) of methylcaprylate and 0.32 g (6 mmol) of sodium methoxide. The mixture wasimmersed in a 185-195° C. oil bath and heated for 58 hours. Aftercooling to 75° C. and addition of 0.35 g (6 mmol) of acetic acid theflask was cooled further and residual methyl caprylate (17 g) removed bydistillation at 48-67° C./0.8 mm, followed by caprolactam (10 g) at90-95° C./0.8 mm. The residue was diluted with methylene chloride,washed with water to further remove caprolactam, dried (MgSO₄),filtered, and evaporated under reduced pressure to give compound D (6.3g, 38% yield based on unrecovered caprolactam) as a light brown wax. Thestructure of the material was confirmed by ¹H NMR analysis. ¹H NMR(CDCl₃): δ 5.60 (br m, 1H, NH); 3.62 (s, 3H, CH₃—OCO); 3.20 (app q, 2H,—CH ₂—NH—); 2.25 (t, 2H, —CH₂COO—); 2.16 (t, 2H, —CH ₂CONH—); 1.70-1.18(m, 16H, CH₂(CH ₂)₃CH₂, CH₂(CH ₂)₅CH₃).

[0280] Synthesis of a Mixture of Compound E and F:

[0281] To a 50 mL thick-walled reaction vessel equipped with a magneticstir bar and a Teflon screw cap was added 10.6 g (53.7 mmol) oflaurolactam, 9.83 g (56.4 mmol) of dibutyl carbonate, and 0.58 g (10.7mmol) of sodium methoxide The mixture was immersed in a 120° C. oil bathand heated for 2 hours. After cooling to room temperature the mixturewas diluted with 100 mL of methylene chloride and to it was added 0.67 g(11.2 mmol) of acetic acid. Filtration and solvent removal by rotaryevaporation, followed by further solvent removal in vacuo (<1 mm) at 95°C. gave the product as an off-white paste. ¹H NMR (CDCl₃) indicated thepresence of mainly two compounds, E and F, in an approximately 80:20mole ratio. Flash chromatography (3.5% methanol/methylene chloride) gavepure samples of the two components.

[0282] Compound E:

[0283]¹H NMR (CDCl₃): δ 4.61 (br s, 1H, NH) 4.05 (q, 4H, —CH₂CH ₂—OCO);3.16 (br dt, 2H, —CH ₂—NH—); 2.28 (t, 2H, -2H, —CH₂COO); 1.65-1.21 (m,26H, CH₂(CH ₂)₉CH₂, (CH ₂)₂CH ₃), 0.93 (t, 6H, CH ₃).

[0284] Compound F:

[0285]¹H NMR (CDCl₃): δ 5.50 (br t, 1H, —CH₂ NHCOCH₂); 4.65 (br s, 1H—CH₂ NHCOOCH₂ 4.05 (q, 4H, —CH₂CH ₂—OCO); 3.21 (dt 2H, —CH ₂ NHCOCH₂—);3.16 (br dt, 2H, —CH ₂NHCOOCH₂); 2.28 (t, 2H, —CH₂COO); 2.15 (t, 2H, —CH₂CONH); 1.65-1.21 (M, 26H, CH₂(CH ₂)₉CH₂, (CH ₂)₂CH ₃), 0.93 (t, H, CH₃).

[0286] The lower temperature reaction of these reactants gives little orno compound F.

[0287] Synthesis of a Mixture of Compound G and H:

[0288] To a 50 mL thick-walled reaction vessel equipped with a magneticstir bar and a Teflon screw cap as added 6.06 g (53.7 mmol) ofcaprolactam, 9.83 g (56.4 mmol) of dibutyl carbonate, and 0.58 g (10.7mmol) of sodium methoxide. The mixture was immersed in a 129° C. oilbath and heated for 2 hours. After cooling to room temperature themixture was diluted with 100 mL of methylene chloride and to it wasadded 0.67 g (11.2 mmol) of acetic acid. Filtration and solvent removalby rotary evaporation, followed by further solvent removal in vacuo (<1mm) at 95° C. gave the product as a yellow paste. ¹H NMR (CDCl₃)indicated the presence of compounds G and H in an approximately 80:20mole ratio.

[0289] The lower temperature reaction of these reactants gives little orno compound H.

[0290] Synthesis of a Mixture of Compound I and J:

[0291] To a 25 thick-walled reaction vessel equipped with a magneticstir bar and a Teflon screw cap was added 2.26 g (20 mmol) ofcaprolactam, 1.89 g (21 mmol) of dimethyl carbonate, and 54 mg (1.0mmol) of sodium methoxide. The mixture was immersed in a 130° C. oilbath and heated for ½ hour. After cooling to room temperature themixture was diluted with 100 mL of methylene chloride and to it wasadded 0.67 g (11.2 mmol) of acetic acid. Filtration and solvent removalby rotary evaporation, followed by further solvent removal in vacuo (<1mm) at 95° C. gave the product as a yellow paste. ¹H NMR (CDCl₃)indicated the presence of compounds I and J in an approximately 80:20mole ratio.

[0292] The lower temperature reaction of these reactants gives little orno compound J.

[0293] The synthesis of a mixture of Compounds E and F, G and H, and Iand J show that, especially at higher temperatures, the multifunctionalcarbonyl compound can be formed by nucleophilic acyl addition of alactam anion at the carbonyl of a carbonate to produce an intermediatefollowed by reaction of a second lactam anion at the lactam carbonyl ofthe intermediate. The resulting multifunctional carbonyl compounds canthen be reacted with a 4-aminopiperidine radical to provide a HALSmixture which is an effective stabilizer. Generally the product producedin the lower temperature reactions are less colored.

Example 1 Preparation of 2,2,6,6-tetramethylpiperidin-4-yl6-(2,2,6,6-tetramethyl-4-piperidinoxycarbonyl amino)hexanoate (CompoundI)

[0294] To a 500 mL three-necked flask equipped with a magnetic stirrer,a Dean-Stark trap with a condenser, a thermometer, and a glass stopperwas added 20 g (98.4 mmol) of Compound A, 46.3 g (0.295 mol) of2,2,6,6-tetramethyl-4-piperidinol, and 150 mL of toluene. Under a slownitrogen flow, 20 mL of toluene was distilled off and the trap drained.The glass stopper was removed and 1.0 g (1.67 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added. Another 75 mL oftoluene was slowly distilled off over 8 hours. After addition of another110 mL of toluene, 80 mL of toluene was removed over an additional 2hours. The degree of conversion by NMR analysis was >98%. The mixturewas cooled to room temperature and diluted with ether. The organicsolution was washed with water to remove excess amino alcohol and driedover sodium carbonate. Filtration and removal of solvent under reducedpressure followed by further solvent removal in vacuo (<1 mm) at 95° C.gave 41.2 g (92%) of Compound I as an white solid, m.p. 59-62° C. Thestructure of the material was confirmed by ¹H NMR analysis. ¹H NMR(CDCl₃): δ 5.19 (m, 1H, R₂CH—OCOCH₂—); 5.05 (m, 1H, R₂CHOCONH—); 4.63(br s, 1H, NH); 3.17 (br dt, 2H, —CH ₂—NH—); 2.28 (t, 2H, —CH₂COO);2.00-1.30 (m, 14H, CH ₂C(CH₃)₂, CH(CH ₂)₃CH₂, 1.20 (d, 24H, CH₂C(CH₃)₂).

Example 2 Preparation of 1,2,2,6,6-pentamethylpiperidin-4-yl6-(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonylamino)hexanoate (CompoundII)

[0295] To a 100 mL three-necked flask equipped with a magnetic stirrer,a Dean-Stark trap with a condenser, a thermometer, and a glass stopperwas added 4.85 g (23.9 mmol) of Compound A, 12.2 g (71.6 mmol) of1,2,2,6,6-pentamethyl-4-piperidinol, and 30 mL of toluene. Under a slowargon flow, 17 mL of toluene was distilled off and the trap drained. Theglass stopper was removed and 0.26 g (0.43 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added. Another 22 mL oftoluene was slowly distilled off over 1 hour. After addition of another10 mL of toluene, 11 mL of toluene was removed over an additional 3hours. The degree of conversion by NMR analysis was >97%. The mixturewas cooled to room temperature and diluted with ethyl acetate. Theorganic solution was washed with water to remove excess amino alcoholand dried over magnesium sulfate. Filtration and removal of solventunder reduced pressure followed by further solvent removal in vacuo (<1mm) at 95° C. gave 10.23 g (89%) of Compound II as a nearly colorlessviscous oil. The structure of the material was confirmed by ¹H NMRanalysis. ¹H NMR (CDCl₃): δ 5.03 (m, 1H, R₂CH—OCOCH₂—); 4.92 (m, 1H,R₂CHOCONH—); 4.68 (br s, 1H, NH); 3.18 (br dt, 2H, —CH ₂—NH—); 2.28 (t,2H, —CH₂COO—); 2.23 (s, 3H, CH₃NC(CH₃)₂); 1.90-1.35 (in, 14H, CH₂(CH₂)₃CH₂, CH ₂C(CH₃)₂), 1.13 (d, 24H, CH₂C(CH ₃)₂). The TGA T-10% value ofCompound II was 237° C.

Example 3 Preparation of 2,2,6,6-tetramethylpiperidin-4-yl6-(2,2,6,6-tetramethyl-4-piperidinoxycarbonylamino)undecanoate (CompoundIII)

[0296] A 250 mL single-necked reaction flask was equipped with amagnetic stirrer and a distillation head fitted with a thermometer,condenser, and receiving flask with a nitrogen inlet and outlet to abubbler. To this flask was charged 4.3 g (11.57 mmol) of Compound B,7.27 g (46.3 mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and 200 mL ofxylene. Under a slow nitrogen flow, 25 mL of xylene was distilled offand the trap drained. After lowering the heat source and allowing themixture to cool to 110° C., 0.17 g (0.28 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added and the heatsource raised. Another 290 mL of xylenes were slowly distilled off over7 hours, charging 100 mL of xylenes at the 3 hour point. After additionof another 240 mL of xylenes, distillation was continued for another 12hours, during which time 175 mL was collected. NMR analysisindicated >90% conversion. The mixture was cooled to room temperatureand diluted with ether. The organic solution was washed with water toremove excess amino alcohol and dried over magnesium sulfate. Filtrationand removal of solvent under reduced pressure followed by furthersolvent removal in vacuo (<1 mm) at 95° C. gave 5.5 g (83%) of CompoundIII as a yellow oil. The structure of the material was confirmed by ¹HNMR analysis. ¹NMR (CDCl₃): δ 5.19 (m, 1H, R₂CH—OCOCH₂—); 5.06 (m, 1H,R₂CHOCONH—); 4.62 (br s, 1H, NH); 3.17 (br dt, 2H, —CH ₂—NH—); 2.25 (t,2H, —CH₂COO); 2.00-1.20 (m, 26H, CH ₂C(CH₃)₂, CH₂(CH ₂)₉CH₂), 1.20 (d,24H, CH₂C(CH ₃)₂).

Example 4 Preparation of 1,2,2,6,6-pentaamethylpiperidin-4-yl6-(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonylamino)undecanoate(Compound IV)

[0297] A 250 mL single-necked reaction flask was equipped with amagnetic stirrer and a distillation head fitted with a thermometer,condenser, and receiving flask with a nitrogen inlet and outlet to abubbler. To this flask was charged 4.5 g (12.1 mmol) of Compound B, 8.3g (48.4 mmol) of 1,2,2,6,6-pentamethyl-4-piperidinol, and 200 mL ofxylene. Under a slow nitrogen flow, 25 mL of xylene was distilled offand the trap drained. After lowering the heat source and allowing themixture to cool to 110° C., 0.19 g (0.31 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added. Another 450 mLof xylenes were distilled off over 24 hours, adding 100 mL, 100 mL and150 mL at the 5, 21 and 23 hour points, respectively. The mixture wascooled to room temperature and diluted with ether. The organic solutionwas washed with water to remove excess amino alcohol, followed bywashing with aqueous NaOH and then more water, and finally dried overmagnesium sulfate. Filtration and removal of solvent under reducedpressure followed by further solvent removal in vacuo (<1 mm) at 95° C.gave 5.4 g (79%) of Compound IV as a nearly colorless oil. The structureof the material was confirmed by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 5.05(m, 1H, R₂CH—OCOCH₂—); 4.94 (m, 1H, R₂CH—OCONH—); 4.65 (br s, 1H, NH);3.16 (br dt, 2H, —CH ₂—NH—); 2.25 (t, 2H, t, 2H, —CH₂COO—); 2.23 (5, 3H,CH₃NC(CH₃)₂); 1.90-1.28 (m, 26H, CH₂(CH ₂)₉CH₂, CH ₂C(CH₃)₂), 1.10 (d,24H, CH₂C(CH ₃)₂).

Example 5 Preparation of 2,2,6,6-tetramethylpiperidin-4-yl6-[(2,2,6,6-tetramethyl-4-piperidinyloxy)oxoacetyl]amino hexanoate(Compound V)

[0298] A 250 mL single-necked reaction flask was equipped with amagnetic stirrer and a Dean-Stark trap fitted with a condenser andnitrogen inlet/outlet. The flask was charged with 10.0 g (43.3 mmol) ofcompound C, 20.4 g (130 mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and150 mL of toluene. Under a slow nitrogen flow, 15 mL of toluene wasdistilled off and the trap drained. After lowering the heat source andallowing the mixture to cool to 110° C., 0.46 g (0.76 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added and the heatsource raised. Another 110 mL of toluene was slowly distilled off over 9hours, then 25 mL of xylenes were added and 20 mL of additional solventdistilled off over 6 hours. The resulting mixture was cooled to roomtemperature and diluted with ethyl acetate. The organic solution waswashed with water to remove excess amino alcohol and dried overmolecular sieves. Filtration and removal of solvent under reducedpressure followed by further solvent removal in vacuo (<1 mm) at 95° C.gave 13.0 g (62%) of Compound V as a yellow oil. The structure of thematerial was confirmed by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 7.15 (m,1H, NHCO—); 5.32 (m, 1H, R₂CHOCO—); 5.20 (m, 1H, R₂CHOCO—); 3.38 (dt,2H, —CH ₂—NH—); 2.28 (t, 2H, —CH₂COO—); 2.05-1.10 (m, 14H, CH₂(CH₂)₃CH₂), CH ₂C(CH₃)₂), 1.20 (d, 12H, CH₂C(CH ₃)₂); 1.18 (d, 12H, CH₂C(CH₃)₂).

Example 6 Preparation of 2,2,6,6-tetramethylpiperidin-4-yl6-(octanoylamino)hexanoate (Compound VI)

[0299] A 250 mL single-necked reaction flask was equipped with amagnetic stirrer and a Dean-Stark trap fitted with a condenser andnitrogen inlet/outlet. To this flask was charged 6.1 g (22.5 mmol) ofcompound D, 5.29 g (33.7 mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and150 mL of toluene. Under a slow nitrogen flow, 8 mL of toluene wasdistilled off and the trap drained. After lowering the heat source andallowing the mixture to cool to 110° C., 0.17 g (0.28 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added and the heatsource raised. Another 100 mL of toluene was slowly distilled off over16 hours and the resulting mixture was cooled to room temperature anddiluted with methylene chloride. The organic solution was washed withwater to remove excess amino alcohol and dried over anhydrous sodiumcarbonate. Filtration and removal of solvent under reduced pressurefollowed by further solvent removal in vacuo (<1 mm) at 60° C. gave 8.0g (90%) of Compound VI as a light brown wax. The structure of thematerial was confirmed by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 5.60 (m,1H, NHCO—); 5.18 (m, 1H, R₂CHOCO—); 3.25 (dt, 2H, —CH ₂—NH—); 2.28 (t,2H, —CH₂COO—); 2.16 (t, 2H, —CH₂CONH—); 1.95-1.10 (m, 20H, CH₂(CH₂)₃CH₂, CH₂(CH ₂)₅, CH₂CH₂C(CH₃)₂); 1.20 (d, 12H, CH₂C(CH ₃)₂; 0.88 (t,3H, —CH₂CH ₃).

Example 7 Synthesis of Oligomeric HALS Compounds (Compounds VII andVIII)

[0300] To a 100 ml 3-necked round bottom flask equipped with a magneticstirrer, a thermometer and a Dean-Stark trap fitted with a condenser anda nitrogen inlet/outlet to a bubbler was charged 5.45 g (26.8 mmol) ofCompound A, 27 mL of toluene, 163 mg (0.27 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane, and 5.4 g ofN-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol. The mixture washeated so that 13 mL of solvent distilled off over three hours. A 12 mLaliquot was removed from the reaction mixture (Fraction A), and wasworked up as described below. The remaining reaction mixture was heatedfor an additional 2.5 hours, over which time 8 mL of solvent distilledoff. After addition of 10 mL of xylenes, the temperature was increasedso that 15 mL of additional solvent distilled off over 3 hours. Theresulting reaction mixture (Fraction B) was worked up as describedbelow.

[0301] Workup of Fraction A:

[0302] The 12 mL aliquot was diluted with methylene chloride, washedwith water, dried (MgSO₄), filtered, and the solvent removed underreduced pressure. Further solvent removal in vacuo (<1 mm) at 50-60° C.gave 4.4 g of compound VII as a clear colorless semisolid. HighPerformance Size-Exclusion Chromatography (HPSEC) gave a value of 2,000for the number average molecular weight (Mn) of the material using apolystyrene standard. The structure of the material was confirmed by ¹HNMR analysis. ¹H NMR (CDCl₃): δ 5.07 (m, 0.5H, R₂CH—OCOCH₂—); 4.94 (m,0.5H, R₂CHOCONH—); 4.65 (br s, 1H, NH); 3.92 (app q, 2H, —CH ₂—OCOCH₂,—CH ₂—OCONH—); 3.68 (s, 0.44H, —CH₂COOCH ₃); 3.66 (s, 0.44H, —NHCOOCH₃); 3.18 (br m, 2H, —CH ₂—NH—); 2.65 (t, 2H, CH₂CH ₂—N); 2.28 (app q,2H, CH₂COO—); 1.90-1.30 (m, 12H, CH₂(CH ₂)₃CH₂), CH ₂C(CH₃)₂), 1.10 (d,12H, CH₂C(CH ₃)₂).

[0303] Workup of Fraction B:

[0304] The remainder of the reaction mixture was diluted with methylenechloride, washed with water, dried (MgSO₄), filtered, and the solventremoved under reduced pressure. Further solvent removal in vacuo (<1 mm)at 80-90° C. gave 4.6 g of compound VIII as a white foam. HighPerformance Size-Exclusion Chromatography (HPSEC) gave a value of 8,800for the number average molecular weight (Mn) of the material using apolystyrene standard. The structure of the material was confirmed by ¹HNMR analysis. ¹H NMR (CDCl₃): δ 5.07 (m, 0.5H, R₂CH—OCOCH₂—); 4.94 (m,0.5H, R₂CHOCONH—); 4.65 (br s, 1H, NH); 3.92 (app q, 2H, —CH ₂—OCOCH₂,—CH ₂—OCONH—); 3.68 (s, 0.16H, —CH₂COOCH ₃); 3.66 (s, 0.16H, —NHCOOCH ₃;3.18 (br m, 2H, —CH ₂—NH—); 2.65 (t, 2H, CH₂CH ₂—N); 2.28 (app q, 2H,—CH₂COO—); 1.90-1.30 (m, 12H, CH₂(CH ₂)₃CH₂), CH ₂C(CH₃)₂), 1.10 (d,12H, CH₂C(CH ₁₃)₂).

Example 8 Single Step Reaction to Produce2,2,6,6-tetramethyl-4-piperidine6-(2,2,6,6-tetramethyl-4-piperidinoxycarbonyl amino)hexanoate (CompoundI), Base Catalyzed

[0305] To a 100 mL three-necked round bottom flask equipped with amagnetic stir bar, an addition funnel containing anhydrous toluene, anda Dean-Stark trap fitted with a condenser and a nitrogen inlet/outlet,was charged 1.69 g (15 mmol) of caprolactam, 2.74 g (15.75 mmol) ofdibutyl carbonate, 4.94 g (31.5 mmol) of2,2,6,6-tetramethyl-4-piperidinol, and 50 mL of toluene. The mixture washeated to a heating mantle temperature of 142° C., so that 6 mL ofsolvent distilled into the trap. The mixture was cooled and 75 mg (1.39mmol) of sodium methoxide was added to the mixture. The mixture wasreheated to boiling and 20 mL distilled into the trap over 4 hours. Thetrap was drained and 25 mL of toluene was added to the mixture throughthe addition funnel. After another 25 mL of solvent distilled off over 4hours, 25 mL of anhydrous xylenes was added, and 35 mL of solventremoved over 6 hours. ¹H NMR indicated >95% conversion of startingmaterial. Cooling to room temperature, dilution with methylene chloride,washing with water, drying (molecular sieves), filtration, and removalof solvent under reduced pressure gave a yellow oil. Further removal ofvolatiles at 90° C./0.8 mm gave 5.0 g, 75% yield, of a light yellowsemisolid. ¹H NMR indicated the presence of the desired hindered amine,compound I, with approximately 85% purity.

Example 9 Single Step Reaction to Produce2,2,6,6-tetramethyl-4-piperidine6-(2,2,6,6-tetramethyl-4-piperidinoxycarbonyl amino)hexanoate (CompoundI), Lewis Acid Catalyzed

[0306] To a 250 mL three-necked round bottom flask equipped with amagnetic stir bar, and a Dean-Stark trap fitted with a condenser and anitrogen inlet/outlet, was charged 16.9 g (150 mmol) of caprolactam,39.2 g (225 mmol) of dibutyl carbonate, 70.65 g (450 mmol) of2,2,6,6-tetramethyl-4-piperidinol, and 200 mL of toluene. The mixturewas heated to a pot temperature of 120° C., so that 12 mL of solventdistilled into the trap. The mixture was cooled, and 0.85 g (3 mmol) oftitanium (IV) isopropoxide was added to the mixture. The mixture wasreheated to boiling and the pot temperature gradually increased from120° C. to 210° C. so that solvent distilled off over 20 hours. ¹H NMRindicated >95% conversion of starting material. The trap was removed andthe flask fitted with a distillation head and a condenser with a steamjacket. A solid impurity (28.0 g) distilled over at 75-120° C./0.8 mm.The flask residue was diluted with methylene chloride and to it wasadded 0.3 mL of water. Overnight stirring at room temperature,filtration, and removal of solvent gave 59.0 g (89% yield) of a thick,light yellow oil. ¹H NMR indicated the presence of the desired hinderedamine I with approximately 90% purity. To this oil was added 30 ghexanes and the mixture heated until homogeneous. After cooling to 5° C.and standing 12 hours at this temperature, filtration afforded 36 g (53%yield) of the desired hindered amine I as a white solid, mp 51-54° C.,with a purity by ¹H NMR of approximately 95%.

Example 10 Preparation of Oligomeric HALS from BPIP and Compound ACompound (IX)

[0307] To a 250 mL 3-necked round bottom flask equipped with a magneticstirrer, a thermometer, and a Dean-Stark trap fitted with a condenserand nitrogen inlet/outlet to a bubbler, was charged 5.0 g (24.6 mmol) ofCompound A, 100 mL of mixed xylenes, and 9.69 g (24.6 mmol) ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine (BPIP).The mixture was heated to reflux for one hour, after which the heatsource was lowered, the Dean-Stark trap drained of 30 mL of xyleneswhich had collected, and 0.22 g (0.37 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added. The mixture wasreheated to the boiling point, and another 50 mL of solvent was allowedto collect over several hours. Another 100 mL portion of anhydrousxylenes was added and distilled off over several hours. The mixture wascooled to room temperature, diluted with methylene chloride, washed withwater, dried (molecular sieves), filtered and the solvent removed underreduced pressure to give 12.1 g of compound IX as a tacky yellowishsolid.

[0308] wherein i and j are integers and the sum of i and j is greaterthan or equal to 2. The structure of compound IX was confirmed with ¹HNMR analysis. ¹H NMR (CDCl₃): δ 4.58 (br m, NH); 4.35 (m, R₂CHNR ₂);3.65 (s, CH₃O—); 3.25 (app q, —CH ₂—NH—); 3.00 (app q, —CH ₂—NRCO—);2.89 (m, R₂CHNHR); 2.37 (t, 2H, —CH₂COO); 1.90-0.89 (m, N—CH₂(CH ₂)₄CH₂—N, COCH₂(CH ₂)₃CH₂NH, CH ₂C(CH₃)₂, CH₂C(CH₃)₂).

Example 11 Single Step Reaction to Produce Oligomeric HALS fromCaprolactam, N-hydroxyethyl-2,2,6,6-tetramethyl-4-piperidinol, andDibutyl Carbonate

[0309] To a 50 ml three-necked reaction flask, equipped with a magneticstirrer and a Dean-Stark trap fitted with a condensor and nitrogeninlet/outlet, was charged 1.0 g (4.97 mmol) ofN-hydroxyethyl-2,2,6,6-tetramethyl-4-piperidinol, 0.56 g (4.97 mmol) ofcaprolactam, 0.86 g (4.97 mmol) of dibutyl carbonate, 30 mL of toluene,and 40 mg (0.75 mmol) of sodium methoxide. The flask was immersed in anoil-bath and heated so that the solvent was distilled off over 4 hours.20 mL of xylenes was then added to the reaction mixture and 20 mL ofadditional solvent distilled off over 4 hours. The resulting mixture wascooled to room temperature and diluted with dichloromethane. The organicsolution was washed with water, dried (MgSO₄), and filtered. The solventwas then removed under reduced pressure using a rotary evaporator andfurther removed under vacuum (<1 nm of Hg) at 95° C. to give 1.5 g (88%)of compound VII. The structure of compound VII was confirmed by ¹H NMR.

Example 12 Low Temperature Synthesis of Compound A

[0310] To a 250 mL three-neck round bottom flask equipped with amagnetic stirrer, a ground glass stopper, a condenser and nitrogeninlet, and a thermometer was placed 50.33 g (558 mmol) of dimethylcarbonate and 1.04 g (19.3 mmol) of sodium methoxide. The mixture wascooled to 15° C. and 21. 8 g (193 mmol) of caprolactam was added. Themixture was stirred with intermittent cooling to maintain the reactiontemperature between about 9 and 18° C. for 45 minutes, then 2.4 g (40mmol) of glacial acetic acid was added at <19° C. The mixture wasdissolved in 100 mL of methylene chloride and the organic layerextracted with water, dried (MgSO₄), filtered, and the solvent removedunder reduced pressure, followed by further removal in vacuo (<1 mm ofHg) at 95° C. 39.0 g (99%) of Compound A was recovered as a nearlycolorless oil.

Example 13 Preparation of HALS Mixtures by Reaction of2,2,6,6-tetramethyl-4-piperidinol and a Mixture of Compounds E and F

[0311] A 250 mL 3-necked reaction flask was equipped with a magneticstirrer, a thermometer adapter, and a distillation head fitted with acondenser, a receiver, and a nitrogen inlet/outlet. To this flask wascharged 4.3 g (10.45 mmol) of the E/F mixture generated above, 7.27 g(46.3 mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and 200 mL of xylenes.Under a slow nitrogen flow, 10 mL of xylenes were distilled off and thetrap drained. After lowering the heat source and allowing the mixture tocool to 110° C., 0.17 g (0.28 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added and the heatsource raised. Another 172 mL of xylenes were slowly distilled off over12 hours. The resulting mixture was cooled to room temperature anddiluted with ethyl acetate. The organic solution was washed with waterto remove excess amino alcohol and dried over molecular sieves.Filtration and removal of solvent by rotary evaporation, and furthersolvent removal in vacuo (<1 mm) at 95° C. gave 5.6 g (93%) ofcomposition M-1 as a yellow oil. The structure of the compounds in themixture was verified by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 5.41 (br s,NH); 5.19 (m, R₂CH—OCOCH₂—); 5.06 (m, R₂CHOCONH—); 4.62 (br s, NH); 3.22(dt, —CH ₂—NH—); 3.17 (br dt, —CH ₂—NH—); 2.25 (t, —CH₂COO); 2.00-1.20(m, CH ₂C(CH₃)₂, CH₂(CH ₂)₉CH₂), 1.20 (d, CH₂C(CH ₃)₂).

[0312] M-I (R=H)

Example 13 Preparation of HALS Mixtures by Reaction of1,2,2,6,6-pentamethyl-4-piperidinol and a Mixture of Compounds E and F

[0313] A 500 mL 3-necked reaction flask was equipped with a magneticstirrer, a thermometer adapter, and a distillation head fitted with acondenser, a receiver, and a nitrogen inlet/outlet. To this flask wascharged 7.9 g (19.2 mmol) of the E/F mixture generated above, 14.5 g(85.04 mmol) of 1,2,2,6,6-pentamethyl-4-piperidinol, and 300 mL ofxylenes. Under a slow nitrogen flow, 100 mL of xylenes were distilledoff and the trap drained. After lowering the heat source and allowingthe mixture to cool to 100° C., 0.34 g (0.56 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added and the heatsource raised. Another 160 mL of xylenes were slowly distilled off over10 hours. After addition of another 20 mL portion of xylenes, heatingwas continued for 8 hours, over which time 32 mL of xylenes werecollected. The resulting mixture was cooled to room temperature anddiluted with methylene chloride. The organic solution was washed withwater to remove excess amino alcohol and dried over MgSO₄. Filtrationand removal of solvent by rotary evaporation, and further solventremoval in vacuo (<1 mm) at 95° C. gave 11.2 g (96%) of composition M-11as a yellow oil. The structure of the compounds in the mixture wasverified by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 5.42 (br s, 1H, NH); 5.05(m, R₂CH—OCOCH₂—); 4.94 (m, R₂CHOCONH—); 4.65 (br s, NH); 3.22 (dt, —CH₂—NH—); 3.16 (br dt, —CH ₂—NH—); 2.25 (t, —CH₂COO—); 2.23 (s,CH₃NC(CH₃)₂); 1.90-1.28 (m, CH₂(CH ₂)₉CH₂, CH ₂C(CH₃)₂), 1.10 (d,CH₂C(CH ₁₃)₂).

[0314] M-II (R=CH₃)

Performance of HALS Compounds According to the Present InventionExamples 15-21 Weathering Performance of 2 k Acrylic Urethane Clear CoatComposition Containing 1,2,2,6,6-pentamethyl-4-piperidine6-(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonylamino)hexanoate (CompoundII)

[0315] Compound II (1% based on total resin solids) was pre-dissolved inthe solvent mixture (5-10% solids) and added to the clear 2k acrylicurethane formulation given in Table I. The 2 k acrylic urethane is atwo-component urethane formed by reacting a hydroxy functional acrylicpolymer with an isocyanate cross linker. Components I and II were mixedjust before use. The clear coats were applied to cold roll steel panels,measuring 4″×12″ and pre-coated with an E-coat primer and whitebase-coat, obtained from ACT Laboratories, Inc. of Hillsdale, Mich. Thedraw-down technique, using WC-60 WIRE-CATORS™ available from Leneta Co.of Ho-Ho-Kus, N.J., was used to apply the clear coat to the pre-coatedpanels. The clear coats were allowed to flash for 10 min at ambienttemperature and cured for 30 min. at 120° C. TABLE I Acrylic UrethaneClear Coat Formulation Raw Material Amount Component I JONCRYL ® CDX-588Acrylic Resin^(a) 100 parts T-12 (2% Solids in Catalyst Solution)^(b) 5parts Solvent Mixture 45 parts Compound II 1 part^(c) Component IIDESMODUR ® N-3390 (90% Solids)^(d) 33 parts Solvent Mixture 17 partsCatalyst Solution T-12 (Dibutyltin dilaurate)^(b) 1 part Acetic Acid 4parts Propylene glycol methyl ether acetate 45 parts Solvent Mixture:Xylenes 1 part Propylene glycol methyl ether acetate 1 part Methyl amylketone 1 part

[0316] Accelerated weathering was carried out on the coatings with a QUVAccelerated Weather Tester device (commercially available from Q PanelLaboratory Products of Cleveland, Ohio) equipped with UVA-340fluorescent bulbs and with an Atlas Ci65 WeatherOmeter (“Xenon WOM”)(commercially available from Atlas Electronic Devices Co., Chicago,Ill.) equipped with Xenon arc lamps following the SAE J1960 automotiveexterior test protocol. Natural weathering was carried out using 5 degSouth direct weathering in South Florida. Specular properties (gloss anddistinctness of image, or DOI), total color change (Delta E), andyellowing (Delta b) were measured as a function of weathering time.Specular properties were determined as described in ASTM E284 and D253.Color change and yellowing were determined as described in ASTM D2244.

[0317] The performance of Compound II under QUV weathering is summarizedin Examples 15-17. The effect of Compound II on gloss retention is givenin Example 15, the effect on DOI retention is given in Example 16, andthe effect on delta E is given in Example 17. Example 15. QUV Weathering(UVA-340 Bulbs) of a 2k Acrylic Urethane Clear Coat Stabilized withCompound II, Effect on Percent Gloss Retention Exposure (hours)Stabilizer 1527 2500 3006 3508 4014 4495 5000 5500 6002 6500 7011 None102 86 91.9 72.2 65.1 49.9 41.7 42.2 34.0 33.8 2.1 Compound 102 96.898.7 99.7 99.6 98.9 101 99.3 100 99.9 96.2 II

[0318] A 2 k acrylic urethane clear coat stabilized with 1% of CompoundII showed superior percent gloss retention compared to the 2 k urethaneclear coat containing no stabilizer. Example 16. QUV Weathering (UVA-340Bulbs) of a 2k Acrylic Urethane Clear Coat Stabilized with Compound II,Effect on Percent DOI Retention Exposure (hours) Stabilizer 1527 25003006 3508 4014 4495 5000 5500 6002 6500 7011 None 101 97.4 83.7 45.326.1 14 12.9 12.7 8.4 9.1 0.1 Compound 102 101 101 102 106 106 107 107107 107 107 II

[0319] A 2 k acrylic urethane clear coat stabilized with 1% of CompoundII showed superior percent DOI retention compared to the a 2 k urethaneclear coat containing no stabilizer. Example 17. QUV Weathering (UVA-340Bulbs) of a 2k Acrylic Urethane Clear Coat Stabilized with Compound II,Effect on Delta E Exposure (hours) Stabilizer 473 1527 3006 4014 50006002 None 1.19 1.99 3.29 3.51 4.01 4.41 Compound II 0.39 0.63 1.22 1.221.36 1.73

[0320] A 2 k acrylic urethane clear coat stabilized with 1% of CompoundII had a superior effect on total color change (Delta E) compared to thea 2 k urethane clear coat containing no stabilizer. An increase in DeltaE indicates an unfavorable discoloration of the urethane coat.

[0321] In addition to the above properties, a visual evaluation ofblistering was done. After about 7011 hrs, the unstabilized coating wascompletely delaminated while the coating containing Compound II showedno signs of blistering.

[0322] The performance of Compound II under Xenon WOM weathering issummarized in Examples 18-20. The effect of Compound II on glossretention is given in Example 18, the effect of Compound II on DOIretention is given in Example 19, and the effect on delta E is given inExample 20. The effect of Compound II under natural weathering (Florida)on gloss retention, yellowing (delta b), and total color change (deltaE) is given in Example 21. Example 18. Xenon Weathering (SAE J1960Automotive Exterior) of a 2k Polyurethane Acrylic Coating Stabilizedwith Compound II, Effect on Percent Gloss Retention Exposure (hours)Stabilizer 485 987 1513 2011 2517 2947 3539 4039 None 97.3 94.5 95.990.6 76.4 64.2 47.3 34.5 Compound II 96.5 95.0 95.4 96.0 92.7 84.7 73.162.4

[0323] A 2 k acrylic urethane clear coat stabilized with 1% of CompoundII showed superior gloss retention compared to the a 2 k urethane clearcoat containing no stabilizer. Example 19. Xenon Weathering (SAE J1960Automotive Exterior) of a 2k Polyurethane Acrylic Coating Stabilizedwith Compound II, Effect on Percent DOI Retention Exposure (hours)Stabilizer 485 987 1513 2011 2517 2947 3539 4039 4443 5003 None 104 101101 96.4 86.5 76.7 54.2 36.6 24.1 16.6 Compound II 101 102 101 101 10099.6 96.0 93.8 89.0 75.3

[0324] A 2 k acrylic urethane clear coat stabilized with 1% of CompoundII showed superior percent DOI retention compared to the a 2 k urethaneclear coat containing no stabilizer. Example 20. Xenon Weathering (SAEJ1960 Automotive Exterior) of a 2k Polyurethane Acrylic CoatingStabilized with Compound II, Effect on Delta E Exposure (hours)Stabilizer 485 987 1513 2011 2517 2947 3539 4039 4443 5003 None 0.901.08 1.42 2.10 2.42 3.31 3.30 3.68 3.78 4.28 Compound II 0.42 0.54 0.511.06 1.08 2.29 2.24 2.44 2.41 2.45

[0325] A 2 k acrylic urethane clear coat stabilized with 1% of CompoundII had a superior effect on total color change (Delta E) compared to thea 2 k urethane clear coat containing no stabilizer. An increase in DeltaE indicates an unfavorable discoloration of the urethane coating.

[0326] In addition, to the above properties a visual evaluation of thedegree of cracking was done after 5003 hrs. On a scale of 0 to 5, with 0being the best, the unstabilized coating was rated 5 (severe cracking),while the coating stabilized with 1% Compound II was rated 1 (veryslight cracking). Example 21. Florida Weathering (50° South, Direct, 18Months) of a 2k Acrylic Urethane Clear Coat Stabilized with Compound II,Effect on Gloss Retention, Yellowing (Delta b), and Total Color Change(Delta E) Stabilizer % Gloss Delta b Delta E None 93 0.61 0.73 CompoundII (1%) 96 0.13 0.25

[0327] Under natural weathering conditions a 2k acrylic urethane clearcoat stabilized with 1% Compound II showed superior performance in glossretention, yellowing, and total color change compared to the a 2kurethane clear coat containing no stabilizer. An increase in Delta Eindicates an unfavorable discoloration of the urethane coating. Anincrease in Delta b indicates an unfavorable yellowing of the urethanecoating.

Example 22 Comparison of Compound II to Conventional HALS Compounds in aPolypropylene Article

[0328] Compound III and several commercially available HALS compoundswere each dry blended at a 0.25% loading level into PROFAX 6501polypropylene powder containing 0.1% 2,4,6-tri-t-butylphenol(commercially available from Montell USA, Inc. of Wilmington, Del.). Theblends were milled with a steam double roller mill at 160-170° C. forfour minutes at 25 rpm. The samples were then compression molded intofilms at 200° C. for three minutes at a maximum pressure of 30 tons. Thesample thicknesses for the exposure tests were measured for each filmand fell in the range between 2.0 and 2.5 mils. The samples were exposedin a dry Xenon weatherometer and a 120° C. oven. Sample degradation wasfollowed by measurements of the increase in the intensity of thecarbonyl absorption using a Perkin-Elmer 1310 infrared spectrophotometeravailable from Perkin-Elmer Corp. of Norwalk, Conn. Percent carbonyldevelopment was expressed according to the following relationship:

% Carbonyl development=(A _(x) −A _(o))/a*1

[0329] where A_(o)=absorbance at 5.85 microns less absorbance at 5.35microns for the unexposed film

[0330] A_(x)=absorbance at 5.85 microns less absorbance at 5.35 micronsfor the exposed film

[0331] a=0.20 (absorptivity for “carbonyl” in polypropylene)

[0332] 1=film thickness in mils

[0333] The exposure endpoint was defined as exposure hours required toreach a 0.1% carbonyl development level. The data in Table II provide acomparison of Compound II with a variety of other commercially availableHALS compounds. TABLE II Performance of HALS compounds in PROFAX 6501Polypropylene. HALS Compound in PROFAX 6501 Dry XeWOM Oven 120° C.Sample ID Polypropylene (hours)^(a) (days)^(a) A CYASORB ® 1320 36UV-3346^(b) B CHIMASORB ® 944^(c) 1690 51 C TINUVIN ® 783^(c)  987 51 DUVASORB ® HA-88^(d) 1900 51 E UV-CHEK ® >2000  11 AM-340^(e) F TINUVIN ®770^(c) 1200-1600  7 G TINUVIN ® 765^(c) 1200-1600 14 H CompoundII >2000  11 I N/A <400  9

[0334] The data in Table II demonstrate that Compound II outperformedthe unstabilized system and showed equal or superior performancecompared to the other HALS compounds tested after 2000 hours exposure inthe XeWOM .

Comparison of HALS Compounds of the Present Invention to ConventionalHALS Example 23 Performance of Compounds I-IV, VII, and VIII Relative toConventional HALS in a PROFAX 6501 Polypropylene Article

[0335] Compounds I-IV, VII, and VIII, as well as several commerciallyavailable HALS compounds, were each dry blended at a 0.2 percent loadinglevel into a PROFAX 6501 polypropylene powder (commercially availablefrom Montel USA Inc. of Wilmington, Del.) containing 0.07 percentcalcium stearate (commercially available from Witco Corp. of Greenwich,Conn.), and 0.07 percent Cyanox A-2777 (commercially available fromCytec Industries of West Paterson, N.J.). Blended material wasmelt-mixed in a Brabender PL-2000 torque rheometer base (commerciallyavailable from C. W. Brabender Inc., South Hackensack, N.J.) equippedwith a single mixing screw extruder-5 zone, single pass at 50-75 rpm,with the temperature of zones 1-5 at 210° C., 215° C., 220° C., 225° C.,and 230° C., respectively. The extrudate was cooled, dried, andpelletized. Pellets were compression molded into sample plaques(2×2.5×0.100 inches) using a PHI press (commercially available fromPasadena Hydraulics Inc., The City of Industry, Calif.) at 275° C.Sample plaques were exposed in the xenon-arc weatherometer as determinedby ASTM G-26 Standard using Test Method B with alternate exposure tolight and darkness and intermittent exposure to water spray maintainingan atmosphere temperature of 63±3° C. and a relative humidity of 30±5percent (Miami, Fla. conditions). Color (ΔE) was determined with aMacbeth Color Eye Colorimeter (commercially available fromGretag-MacBeth LLC of New Windsor, N.Y.) under laboratory conditionswith illuminate C, 2° observer, specular component excluded, and UVcomponent included. Specular gloss was measured according to ASTM D523Standard using a Gardner black plate 60° Glossmeter measuring deviationloss to 50 percent. Pellets were also injection-molded into tensile barsusing an Arburg “Allrounder” hydraulic injection molder (commerciallyavailable from Arburg GmbH & Co. of Lossburg, Germany). Temperaturesused were as follows: nozzle, 200° C.; nozzle side, 220° C.; middle,225° C.; feed, 210° C.; and mold, 52° C. The blended material was alsomade into thin films. The thin films were prepared as described inExample 22.

[0336] Compounds I-IV, VII, and VIII were compared to Tinuvin 765(bis(1,2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, CAS #41556-26-7)(commercially available from Ciba Specialties Corp., Hawthorne, N.Y.);Tinuvin 770 (bis(2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, CAS#52829-07-9) (commercially available from Ciba Specialties Corp.,Hawthorne, N.Y.); Tinuvin 622(1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl piperidine-succininicacid, dimethyl ester, copolymer, CAS #65447-77-0) (commerciallyavailable from Ciba Specialties Corp., Hawthorne, N.Y.); Chimasorb 944(poly[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4,-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)-imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino], CAS #71878-19-8) (commerciallyavailable from Ciba Specialties Corp., Hawthorne, N.Y.); Tinuvin 783 (a1:1 blend of Chimasorb 944 and Tinuvin 622) (commercially available fromCiba Specialties Corp., Hawthorne, N.Y.).

[0337] Table III shows a comparison of Hours to ΔE=3 and Hours to 50%Gloss Retention for polypropylene plaques and Hours to Failure (asmeasured by carbonyl development in thin films) for the HALS of theinvention and several commercially available HALS. Table IV shows acomparison of 50% Strength Retention, 50% Elongation Retention, andHours to 50% Retention of Tensil Strength for the HALS of the inventionand several commercially available HALS compounds in PROFAXpolypropylene tensile bars. TABLE III Performance of HALS of theInvention Relative to Conventional HALS in PROFAX 6501 PolypropylenePlaques and, Polypropylene Thin Films. Hours to 50% Hours to Hours to ΔE= 3 Gloss Retention Failure* Contained Additive (plaques) (plaques)(thin films) Compound VII 2080  1333 1000  Compound VIII 1267   707 600Tinuvin 622^(a) 529  895 600 None 180 <100 200 Compound II 2300  >1600 Compound IV >3000  >1600  800 Tinuvin 765^(a) 2740  >1600  600 None 180<100 200 Compound I 474 >1200  600 Compound III 600 >600 1000  Tinuvin770^(a) 581 >1200  600 None 180 <100 200

[0338] TABLE IV Performance of HALS of the Invention Relative toConventional HALS in PROFAX 6501 Propylene Tensile Bars, Effect ofFlorida Weathering and Xenon Weathering. Hours to 50% 50% Strength 50%Elongation Retention of Tensile Contained Retention Months RetentionMonths Strength Additive (Florida Weathering) (Florida Weathering)(Xenon Weathering) Compound VII >12  5 Compound VIII 8 5 Tinuvin 622 7 5None <3  <3  Compound II 840 Compound IV 1100  Tinuvin 765 640 None 204Compound I 384 Compound III 690 Tinuvin 770 1000  None 204

[0339] The data in Tables III and IV demonstrate that HALS of theinvention outperformed the unstabilized system and showed equal orsuperior performance compared to the commercially available HALScompounds.

Example 24 Performance of Compounds I-IV, VII-VIII Relative toConventional HALS in Polyethylene Articles

[0340] Compounds I-IV and VII-VIII, as well as several commerciallyavailable HALS compounds were each dry blended at a 0.1 percent loadinglevel into a LLDPE prills (commercially available from EquistarChemicals LP. of Houston Tex.) containing 0.01 percent zinc stearate(commercially available from Malinckrodt Chemicals of St. Louis, Mo.),and 0.07 percent Cyanox A-2777 (commercially available from CytecIndustries of West Paterson, NJ). Blended material was melt-mixed in aBrabender PL-2000 torque rheometer base equipped with a single mixingscrew extruder-5 zone, single pass at 50-75 rpm, with the temperature ofzones 1-5 at 170° C., 175° C., 180° C., 185° C., and 190° C.,respectively. The extrudate was cooled, dried, and pelletized. Pelletswere compression molded into sample plaques (2×2.5×0.100 inches) using aPHI press at 177° C. Sample plaques were exposed in the xenon-arcweatherometer as determined by ASTM G-26 Standard using Test Method Bwith alternate exposure to light and darkness and intermittent exposureto water spray maintaining an atmosphere temperature of 63±3° C. and arelative humidity of 30±5 percent (Miami, Fla. conditions). Color (ΔE)was determined with a Macbeth Color Eye Colorimeter under laboratoryconditions with illuminate C, 2° observer, specular component excluded,and UV component included. The blended material was also made into thinfilms. The thin films were prepared as described in Example 22.

[0341] Table V shows a comparison of Hours to ΔE=3 and Hours to 50%Gloss Retention and Hours to Failure (as measured by carbonyldevelopment) for the HALS of the invention and several commerciallyavailable HALS compounds in LLDPE plaques and thin films. TABLE VPerformance of HALS of the Invention Relative to Conventional HALS inLLDPE Plaques and Thin Films. Hours to 50% Hours to Hours to DE = 3Gloss Retention Failure* Contained Additive (plaques) (plaques) (Thinfilms) Compound VII  6122 5729 1000 Compound VIII  6831 4900 1800Tinuvin 622 >7600 6212 1000 None  180 2467  200 Compound II >7600 >7600 2200 Compound IV >7600 6850 1000 Tinuvin 765 >7600 >7600  1000 None  1802467  200 Compound I >7600 7492 >1800  Compound III >7600 7446 >1800 Tinuvin 770  600 7252 1800 None  180 2467  200

[0342] The data in Tables III and IV demonstrate that HALS of theinvention outperformed the unstabilized system and showed equal orsuperior performance compared to the commercially available HALScompounds.

Example 25 Performance of Compound VIII Relative to Conventional HALS ina Polypropylene Article

[0343] Compound VIII, 1:1 blends of Compound VIII with Cyasorb^(R)UV-3346, Cyasorb^(R) UV-3346, and several commercially available HALScompounds were each dry blended at a 0.2% loading level in PROFAX 6501polypropylene flake (commercially available from Montel USA Inc. ofWilmington, Del.) containing 0.07 percent calcium stearate (commerciallyavailable from Witco Corp. of Greenwich, Conn.), and 0.07 percent CyanoxA-2777 (commercially available from Cytec Industries of West Paterson,N.J.). Blended material was melt-mixed in a Brabender PL-2000 torquerheometer base (commercially available from C. W. Brabender Inc., SouthHackensack, N.J.) equipped with a single mixing screw extruder-5 zone,single pass at 50-75 rpm, with the temperature of zones 1-5 at 210° C.,215° C., 220° C., 225° C., and 230° C., respectively. The extrudate wascooled, dried, and pelletized. Pellets were compression molded intosample plaques (2×2.5×0.100 inches) using a PHI press (commerciallyavailable from Pasadena Hydraulics Inc., The City of Industry, Calif.)at 275° C. Sample plaques were exposed in the xenon-arc weatherometer asdetermined by ASTM G-26 Standard using Test Method B with alternateexposure to light and darkness and intermittent exposure to water spraymaintaining an atmosphere temperature of 63±3° C. and a relativehumidity of 30±5 percent (Miami, Fla. conditions). Specular gloss wasmeasured according to ASTM D523 Standard using a Gardner black plate 60°Glossmeter measuring deviation loss to 50 percent. Example 25:Performance of Compound VIII of the Invention Relative to ConventionalHALS in PROFAX 6501 Polypropylene Plaques. Hours to 50% Gloss AdditiveRetention Compound VIII 2450 Cyasorb UV-3346 2400 1:1 CyasorbUV-3346:Compound VIII >2850  (1:1) Tinuvin 783 2283 Tinuvin 622 2850

[0344] The data in Example 25 demonstrates that HALS of the inventionshowed equal or superior performance compared to commercially availableHALS compounds.

Example 26 Performance of Compounds I and II Relative to ConventionalHALS in Nylon 6 Plaques

[0345] Compounds I and II and several commercially available HALScompounds were each dry blended at a 0.3% loading level into B85ZP Nylon6 (commercially available from Honeywell Inc. of Morris Township, N.J.)containing 0.075% Cyanox A-2777 (commercially available from CytecIndustries Inc. of West Paterson, N.J.). The blended material was meltmixed in a Haake SS (commercially available from Haake Inc. (USA) ofParamus, N.J.) 0.75 inch, 25:1 single mixing screw extruder -4 zone,single pass at 70 rpm, with the temperature of zones 1-4 at 245° C.,260° C., 270° C., and 260° C., respectively. The extrudate was cooleddried and pelletized. Pellets were injection molded into sample plaques(2×2.5×0.100 inches) using an Arburg Allrounder 320-210-750 injectionmolding machine (commercially available from Arburg GmbH & Co. ofLossburg, Germany) with the nozzle at 245° C., nozzle side at 260° C.,middle at 270° C., feed at 270° C., and mold at 82° C. Sample plaqueswere exposed in the xenon-arc weatherometer as determined by ASTM G-26Standard using Test Method B with alternate exposure to light anddarkness and intermittent exposure to water spray maintaining anatmosphere temperature of 63±3° C. and a relative humidity of 30±5percent (Miami, Fla. conditions). Color as measured by yellowing index(YI) and ΔE was determined with a Macbeth Color Eye Colorimeter underlaboratory conditions with illuminate C, 2° observer, specular componentexcluded, and UV component included. Example 26: Performance ofCompounds I and II Relative to Conventional HALS in Nylon 6 Plaques.Additive YI Value after 4000 hours Δ E value UV-3346 6 8.3 UV-3529 5.6 8Nylostab S-EED^(a) 3.3 6.8 Tinuvin 770 3.4 8.3 Compound I 2.3 7.8Compound II 2.4 7.3 None 8.4 12.3

[0346] The data in Example 26 demonstrates that HALS of the inventionoutperformed the unstabilized system and showed equal or superiorperformance compared to the other HALS compounds.

[0347] The invention described and claimed herein is not to be limitedin scope by the specific embodiments herein disclosed, since theseembodiments are intended as illustrations of several aspects of theinvention. Any equivalent embodiments are intended to be within thescope of this invention. Indeed, various modifications of the inventionin addition to those shown and described herein will become apparent tothose skilled in the art from the foregoing description. Suchmodifications are also intended to fall within the scope of the appendedclaims.

What is claimed is:
 1. A compound having the formula (I):RZ—CO—CR^(a)R^(b)—(CR^(c)R^(d))_(n)—NH—(Y)_(m)—CO—A  (I) wherein n is aninteger from 1 to 15, m is either 0 or 1; R^(a), R^(b), R^(c), and R^(d)are each a hydrogen or a hydrocarbyl group; Y is CO—(CR^(e)R^(f))_(p),wherein R^(e) and R^(f) are each a hydrogen or hydrocarbyl group and pis zero or an integer from 1 to 20 or CO—C₆H₄—, wherein the substitutionpattern on the phenylene group is an ortho, meta, or para substitutionpattern and one or more of the hydrogens of the phenylene group may besubstituted by a hydrocarbyl group or a functional group; Z is —O— or—NG—, wherein G is H, C₁-C₁₂ alkyl or the radical R; wherein R is

wherein R¹ is hydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy,C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy,C₃-C₆ alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted orsubstituted on the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphaticC₁-C₈ acyl; R² is hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal Rmoieties, which together with the carbon to which they are attached forma C₅-C₁₀ cycloalkyl; and A is either ZR or a hydrocarbyl group.
 2. Thecompound of claim 1, wherein R¹ is a H, C₁-C₄ alkyl, O, OH; C₁-C₁₈alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₋₂ cycloalkoxy,C₅-C₁₂hydroxycycloalkoxy; R² is H, or C₁-C₄ alkyl; R³, R⁴, R⁵, and R⁶are each H or C₁-C₄ alkyl; R^(a), R^(b), R^(c), and R^(d), are each ahydrogen, aromatic, or C₁-C₄ alkyl; and n is from 4 to
 11. 3. Thecompound of claim 1, wherein R¹ is H or CH₃; R³, R⁴, R⁵, and R are eachCH₃; R² is hydrogen; R^(a), R^(b), R^(c) and R^(d) are each a hydrogen;Z is —O—; m is 0 or 1; and n is and integer from 4 to
 10. 4. Thecompound of claim 3 wherein A is ZR.
 5. The compound of claim 4 whereinn is
 4. 6. A method of forming the compound of claim 1 comprising:combining one or more multi-functional carbonyl compounds of generalstructure: DO—CO—CR^(a)R^(b)—(CR^(c)R^(d))_(n)—NH—(Y)^(m)—CO—B wherein nis an integer from 1 to 15, m is either 0 or 1; R^(a), R^(b), R^(c), andR^(d), are each a hydrogen or a hydrocarbyl group; Y isCO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f) are each a hydrogen orhydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C₆H₄—,wherein the substitution pattern on the phenylene group is an ortho,meta, or para substitution pattern and wherein one or more of thehydrogens of the phenylene group may be substituted by a hydrocarbylgroup or a functional group; D is a hydrocarbyl group; and B is eitherOD or D; with one or more 1-substituted piperidin-4-ol or4-aminopiperidines of general structure

wherein Z is OH or NHG, wherein G is as defined in claim 1; R¹ ishydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy, C₃-C₆alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted or 2substituted on the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphaticC₁-C₈ acyl; R² represents hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵,and R⁶ are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or twogeminal R moieties, which together with the carbon to which they areattached form a C₅-C₁₀ cycloalkyl, to form a reaction mixture; reactingthe reaction mixture for a sufficient time to form the compound offormula (1); and recovering the compound of formula (I) from thereaction mixture.
 7. The method of claim 6, wherein the one or moremultifunctional carbonyl compounds is present in an amount of about0.025 to 2.5 M and the molar ratio of the one or more multi-functionalcarbonyl compounds to the one or more 1-substituted piperidin-4-ol or4-aminopiperidines is from about 20:1 to 1:5.
 8. The method of claim 6,wherein the substituted 4-piperidin-4-ol is1,2,2,6,6-pentamethyl-4-piperidinol or 2,2,6,6-tetramethyl-4-piperidinoland the multi-functional carbonyl compound is selected from the groupconsisting of methyl 6-(methoxycarbonylamino)hexanoate, butyl6-(butoxycarbonylamino) undecanoate, methyl6-(butoxycarbonylamino)undecanoate, butyl6-(methoxycarbonylamino)undecanoate, methyl6-(methoxycarbonylamino)undecanoate, and combinations thereof.
 9. Themethod of claim 6, wherein the reaction mixture further comprises asolvent.
 10. The method of claim 6, wherein the reaction mixture furthercomprises a catalyst.
 11. The method of claim 10, wherein the catalystcomprises methoxide.
 12. The method of claim 10, wherein the catalystcomprises a Lewis acid selected from the group consisting of aluminumtrichloride, aluminum tribromide, trimethylaluminum, boron trifluoride,boron trichloride, 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane, zincdichloride, titanium tetrachloride, titanium (IV) isopropoxide, tindichloride, tin tetrachloride, a tetraalkoxytitanate, and mixturesthereof.
 13. The method of claim 10, wherein the catalyst is present inan amount of less than about 30 mole percent based on the molar quantityof the multi-functional carbonyl compound.
 14. A method of forming thecompound of claim 1 from a lactam in a single-step comprising: combiningone or more lactams of general structure

wherein n is an integer from 1 to 15 and R^(a), R^(b), R^(c), and R^(d)are each a hydrogen or a hydrocarbyl group with one or more carbonylcompounds of general structure

wherein m is either 0 or 1, D is a hydrocarbyl group and B is ahydrocarbyl group or OD and Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) andR^(f) are each a hydrogen or hydrocarbyl group and p is zero or aninteger from 1 to 20 or CO—C₆H₄—, and the substitution pattern on thephenylene group may be an ortho, meta, or para substitution pattern, andone or more of the hydrogens of the phenylene group may be substitutedby a hydrocarbyl group or other functional group; and one or more1-substituted piperidin-4-ol or 4-aminopiperidines of general structure

wherein Z is OH or NHG, wherein G is as defined in claim 1; R¹ ishydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy, C₃-C₆alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted or substitutedon the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl;R² represents hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ areeach a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal Rmoieties, which together with the carbon to which they are attached,form a C₅-C₁₀cycloalkyl to provide a reaction mixture; reacting thereaction mixture for a sufficient time to form the compound of formula(I); and recovering the compound of formula (I) from the reactionmixture.
 15. The method of claim 14 wherein the carbonyl compound isselected from the group consisting of a dialkyl carbonate, a dialkyloxalate, a dialkyl diester, an alkyl ester, and mixtures thereof. 16.The method of claim 14, wherein the reaction mixture further comprises acatalyst.
 17. The method of claim 16, wherein the catalyst comprises aLewis acid selected from the group consisting of aluminum trichloride,aluminum tribromide, trimethylaluminum, boron trifluoride, borontrichloride, zinc dichloride, titanium tetrachloride, titanium (IV)isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate,and mixtures thereof.
 18. The method of claim 14, wherein the reactionmixture further comprises a solvent.
 19. The method of claim 18, whereinthe concentration of lactam is from about 0.025 to 10 M; the ratio oflactam to carbonyl compound is from about 2:1 to 1:4; the ratio oflactam to 1-substituted piperidin-4-ol or 4-aminopiperidine is fromabout 1:1; to 1:6; and further comprising a catalyst in an amount ofless than about 30 mole percent relative to the amount of carbonylcompound.
 20. The method of claim 16, wherein n is from 3 to 12 and thecatalyst comprises a base catalyst or a Lewis acid.
 21. The method ofclaim 14, wherein the lactam comprises caprolactam.
 22. The method ofclaim 14, wherein the lactam comprises laurolactam.
 23. A method offorming a multi-functional carbonyl compound having the structureDO—CO—CR^(a)R^(b)—(CR^(c)R^(d))_(n)—NH—(Y)_(m)—CO—B wherein n is aninteger from about 1 to 15, m is either 0 or 1; R^(a), R^(b), R^(c), andR^(d) are each a hydrogen or a hydrocarbyl group; Y isCO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f) are each a hydrogen orhydrocarbyl group and p is an integer from about 0 to 20 or CO—C₆H₄—,wherein the substitution pattern on the phenylene group is an ortho,meta, or para substitution pattern and one or more of the hydrogens ofthe phenylene group may be substituted by a hydrocarbyl group or afunctional group; D is a hydrocarbyl group; and B is either OD or D,comprising: combining one or more lactams of general structure

wherein n and R^(a), R^(b), R^(c), and R^(d) are as defined above withone or more carbonyl compounds of general structure

wherein D, B, Y, and m are as defined above; and a Lewis acid catalyst,or a base catalyst to provide a reaction mixture; reacting the reactionmixture for a sufficient time to produce the multi-functional carbonylcompound; and recovering the multi-functional carbonyl compound from thereaction mixture, wherein the temperature of the reaction mixture whensaid base catalyst is used is less than about 20° C.
 24. The method ofclaim 23, wherein n is from about 3 to
 12. 25. The method of claim 23,wherein the Lewis acid catalyst is selected from the group consisting ofaluminum trichloride, aluminum tribromide, trimethylaluminum, borontrifluoride, boron trichloride, zinc dichloride, titanium tetrachloride,titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, atetraalkoxytitanate, and mixtures thereof.
 26. The method of claim 23,wherein the reaction mixture further comprises a solvent.
 27. The methodof claim 23, wherein the lactam comprises caprolactam.
 28. The method ofclaim 23, wherein the lactam comprises laurolactam.
 29. The method ofclaim 23, wherein the temperature of the reaction mixture when said basecatalyst is used is less than 15° C.